Process for producing isomer enriched higher silanes

ABSTRACT

Methods of selectively synthesizing n-tetrasilane are disclosed. N-tetrasilane is prepared by catalysis of silane (SiH 4 ), disilane (Si 2 H 6 ), trisilane (Si 3 H 8 ), or mixtures thereof. More particularly, the disclosed synthesis methods tune and optimize the n-tetrasilane:i-tetrasilane isomer ratio. The isomer ratio may be optimized by selection of process parameters, such as temperature and the relative amount of starting compounds, as well as selection of proper catalyst. The disclosed synthesis methods allow facile preparation of n-tetrasilane.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 16/158,071, filed Oct. 11, 2018, the entire contents of which are incorporated herein by reference.

TECHNICAL FIELD

Methods of selectively synthesizing n-tetrasilane are disclosed. N-tetrasilane is prepared by catalysis of silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), or mixtures thereof. More particularly, the disclosed synthesis methods tune and optimize the n-tetrasilane:i-tetrasilane isomer ratio. The isomer ratio may be optimized by selection of process parameters, such as temperature and the relative amount of starting compounds, as well as selection of proper catalyst. The disclosed synthesis methods allow facile preparation of n-tetrasilane.

BACKGROUND

Polysilanes have been used in a variety of industries.

Vapor deposition of silicon-containing films using polysilanes is disclosed by JP Pat No 3,185,817 to Seiko Epson Corp.; Kanoh et al., Japanese Journal of Applied Physics, Part 1: Regular Papers, Short Notes & Review Papers 1993, 32(6A), 2613-2619; JP Pat No 3,484,815 to Showa Denko KK; and JP Pat App Pub No 2000/031066 to Showa Denko KK, among others.

Epitaxial Si-containing films, such as Si, SiGe, SiC, SiN, and SiO, have been grown using polysilanes as disclosed by Hazbun et al., Journal of Crystal Growth 2016, 444, 21-27; US Pat App Pub No 2017/018427 to Yi-Chiau Huang et al.; US Pat App Pub No 2016/126093 to Dube et al.; and Hart et al., Thin Solid Films 2016, 604, 23-27]; among others.

Polysilanes have also been used to form larger polymers. See, e.g., US Pat App Pub No 2016/0297997 to Forschungzentrum Jülich Gmbh.

Conversion of lower silanes into higher silanes has been studied extensively both for research and for commercial purposes. Catalytic reactions have been studied. See, e.g., U.S. Pat. No. 5,047,569 to Berris; Corey et al., Organometallics, 1991, 10, 924-930; Boudjouk et al., J. Chem. Soc. Chem. Comm. 1991 245-246; U.S. Pat. No. 5,087,719 to Tilley et al.; Woo et al., J. Am. Chem. Soc. 1992, 114, 7047-7055; Ohshita et al., Organometallics 1994 13, 5002-5012; Bourg et al., Organometallics, 1995, 14, 564-566; Bourg et al., Organometallics 1995, 14, 564-566; U.S. Pat. No. 5,700,400 to Ikai et al.; Woo et al., Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. A, 2000, 349, 87; Rosenberg et al., J. Am. Chem. Soc. 2001, 123, 5120-5121; Fontaine et al., Organometallics 2002, 21, 401-408; Kim et al., Organometallics 2002, 21, 2796; Corey et al., Adv. In Org. Chem. 2004, 51, pp. 1-52; Fontaine et al., J. Am. Chem. Soc. 2004, 126, 8786-8794; U.S. Pat. App. Pub. No. 2008/085373 to Karshtedt et al.; Itazaki et al., Angew. Chem. Int. Ed. 2009, 48, 3313-3316; PCT Pub No WO2010/003729 to Evonik Degussa GMBH; Smith et al., Organometallics 2010, 29, 6527-6533; PCT Pub No WO2012/001180 to SPAWNT PRIVATE S.A.R.L.; PCT Pub No WO2013/019208 to Kovio, Inc.; Feigl et al., Chem. Eur. J. 2013, 19, 12526-12536; Tanabe et al., Organometallics 2013, 32, 1037-1043; U.S. Pat. No. 8,709,369 to Brausch et al.; Schmidt et al., Dalton Trans. 2014, 43, 10816-10827; and U.S. Pat. No. 9,567,228 to Matsushita et al.

All these disclosures notwithstanding, commercial use of polysilanes remains elusive.

SUMMARY

Methods of selectively synthesizing n-tetrasilane are disclosed. A liquid Si_(n)H_((2n+2)) reactant, wherein n=1-3, is transformed in the presence of a heterogeneous catalyst to produce a n-Si₄H₁₀:i-Si₄H₁₀ mixture having a ratio ranging from approximately 5:1 to approximately 15:1. Alternatively, the n-Si₄H₁₀:i-Si₄H₁₀ mixture having a ratio ranging from approximately 5:1 to approximately 15:1 may be produced by catalytically converting a liquid Si_(n)H_((2n+2)) reactant, wherein n=1-3. In another alternative, a liquid Si_(n)H_((2n+2)) reactant, wherein n=1-3, is reacted with a heterogeneous catalyst to produce a n-Si₄H₁₀:i-Si₄H₁₀ mixture having a ratio ranging from approximately 5:1 to approximately 15:1. In yet another alternative, a liquid Si_(n)H_((2n+2)) reactant, wherein n=1-3, is contacted with a heterogeneous catalyst to produce a n-Si₄H₁₀:i-Si₄H₁₀ mixture having a ratio ranging from approximately 5:1 to approximately 15:1. Any of these disclosed methods may include one or more of the following aspects:

-   -   the method not utilizing H₂;     -   the Si_(n)H_((2n+2)) reactant being a liquid;     -   the Si_(n)H_((2n+2)) reactant being a mixture of a liquid and a         gas;     -   the Si_(n)H_((2n+2)) reactant being Si₃H₈;     -   the Si_(n)H_((2n+2)) reactant being liquid Si₃H₈;     -   the Si_(n)H_((2n+2)) reactant being a mixture of Si₂H₆ and         Si₃H₈;     -   the Si_(n)H_((2n+2)) reactant being a liquid mixture of Si₂H₆         and Si₃H₈;     -   the Si_(n)H_((2n+2)) reactant being a mixture of gaseous Si₂H₆         and liquid Si₃H₈;     -   the mixture comprising between approximately 0.1% w/w to         approximately 60% w/w Si₃H₈ and between approximately 40% w/w         and 99.9% w/w Si₂H₆;     -   the mixture comprising between approximately 0.1% w/w to         approximately 25% w/w Si₃H₈ and between approximately 75% w/w         and 99.9% w/w Si₂H₆;     -   the mixture comprising between approximately 0.1% w/w to         approximately 10% w/w Si₃H₈ and between approximately 90% w/w         and 99.9% w/w Si₂H₆;     -   converting approximately 20% w/w to approximately 60% w/w of the         Si_(n)H_((2n+2)) reactant;     -   heating the Si_(n)H_((2n+2)) reactant prior to mixing with the         catalyst;     -   mixing the Si_(n)H_((2n+2)) reactant and catalyst to form a         reactant-catalyst mixture;     -   mixing the Si_(n)H_((2n+2)) reactant and catalyst to form a         reactant-catalyst mixture for a time period ranging from         approximately 1 hour to approximately 24 hours;     -   heating the reactant-catalyst mixture to a temperature ranging         from approximately 30° C. to approximately 55° C.;     -   mixing the reactant-catalyst mixture at a temperature ranging         from approximately room temperature to approximately 53° C.;     -   mixing the reactant-catalyst mixture at a temperature ranging         from approximately 15° C. to approximately 50° C.;     -   mixing the reactant-catalyst mixture at a temperature ranging         from approximately 15° C. to approximately 30° C.;     -   filtering the reactant-catalyst mixture to separate any solids         from the resulting Si_(a)H_((2a+2)) mixture, wherein n=1-6;     -   heating the Si_(n)H_((2n+2)) reactant prior to flowing through a         reactor containing the catalyst;     -   heating the Si_(n)H_((2n+2)) reactant prior to flowing through         the catalyst;     -   flowing the Si_(n)H_((2n+2)) reactant through a reactor         containing the catalyst;     -   flowing the Si_(n)H_((2n+2)) reactant through a reactor         containing the catalyst on glass wool;     -   flowing the Si_(n)H_((2n+2)) reactant through a reactor         containing catalyst pellets;     -   flowing the Si_(n)H_((2n+2)) reactant through a reactor         containing the catalyst to produce a Si_(a)H_((2a+2)) mixture,         wherein a=1-6;     -   the Si_(n)H_((2n+2)) reactant having a residence time in the         reactor ranging from approximately 200 seconds to approximately         600 seconds;     -   heating the reactor to a temperature ranging from approximately         15° C. to approximately 170° C.;     -   heating the reactor to a temperature ranging from approximately         15° C. to approximately 150° C.;     -   heating the reactor to a temperature ranging from approximately         15° C. to approximately 100° C.;     -   heating the reactor to a temperature ranging from approximately         15° C. to approximately 50° C.;     -   heating the reactor to a temperature ranging from approximately         20° C. to approximately 150° C.;     -   heating the reactor to a temperature ranging from approximately         50° C. to approximately 100° C.;     -   heating the reactor to a temperature ranging from approximately         40° C. to approximately 150° C.;     -   maintaining the reactor at a pressure ranging from approximately         10 psig (69 kPa) to approximately 50 psig (345 kPa);     -   the method not requiring a quenching agent;     -   recycling unreacted Si_(n)H_((2n+2)) reactant;     -   isolating the n-Si₄H₁₀:i-Si₄H₁₀ mixture from a Si_(n)H_((2n+2))         mixture, wherein n=1-6;     -   the ratio of n-Si₄H₁₀:i-Si₄H₁₀ ranging from approximately 7:1 to         approximately 15:1;     -   fractionally distilling the n-Si₄H₁₀:i-Si₄H₁₀ mixture to produce         approximately 90% w/w to approximately 100% w/w n-Si₄H₁₀;     -   fractionally distilling the n-Si₄H₁₀:i-Si₄H₁₀ mixture to produce         approximately 95% w/w to approximately 100% w/w n-Si₄H₁₀;     -   fractionally distilling the n-Si₄H₁₀:i-Si₄H₁₀ mixture to produce         approximately 98% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the heterogeneous catalyst comprising an element selected from         the group consisting of Group I, II, and III of the Periodic         Table;     -   the heterogeneous catalyst comprising an element selected from         Group I of the Periodic Table;     -   the heterogeneous catalyst comprising Na;     -   the heterogeneous catalyst comprising K;     -   the heterogeneous catalyst comprising an element selected from         Group III of the Periodic Table;     -   the heterogeneous catalyst comprising Al;     -   the heterogeneous catalyst comprising both an element selected         from Group I and an element from Group III of the Periodic         Table;     -   the heterogeneous catalyst comprising Na and Al;     -   the heterogeneous catalyst comprising Li and Al;     -   the heterogeneous catalyst being selected from a Group I, II or         III element or oxides, alkyls, hydrides, silanides, or silyl         amides thereof;     -   the heterogeneous catalyst being an oxide catalyst;     -   the heterogeneous catalyst being a Group I metal oxide catalyst;     -   the heterogeneous catalyst being Na₂O;     -   the heterogeneous catalyst being K₂O;     -   the heterogeneous catalyst being K, K₂O, or combinations         thereof;     -   the heterogeneous catalyst being Na, Na₂O, or combinations         thereof;     -   the heterogeneous catalyst being a hydride catalyst;     -   the hydride catalyst being selected from the group consisting of         NaH, KH, RbH, CsH, MgH₂, CaH₂, SrH₂, BaH₂, {AlH₃}_(n), AlH₃(L),         {GaH₃}_(n), GaH₃(L), and combinations thereof, wherein n is 1,         2, or 3 and L is NR₃, with each R independently C_(m)H_(2m+1)         and m=1-10;     -   the hydride catalyst being NaH;     -   the hydride catalyst being KH;     -   the hydride catalyst being RbH;     -   the hydride catalyst being CsH;     -   the hydride catalyst being MgH₂;     -   the hydride catalyst being CaH₂;     -   the hydride catalyst being SrH₂;     -   the hydride catalyst being BaH₂;     -   the hydride catalyst being {AlH₃}_(n), wherein n is 1, 2, or 3;     -   the hydride catalyst being {AlH₃};     -   the hydride catalyst being {AlH₃}₂;     -   the hydride catalyst being {AlH₃}₃;     -   the hydride catalyst being AlH₃(L), wherein L is NR₃, with each         R independently C_(m)H_(2m+1) and m=1-10;     -   the hydride catalyst being AlH₃(L), wherein L is a substituted         ethylenediamine;     -   the hydride catalyst being AlH₃(L), wherein L is         N,N,N′,N′-tetramethyl-ethylenediamine;     -   the hydride catalyst being AlH₃(L), wherein L is         N,N,N′,N′-tetramethyl-propanediamine;     -   the hydride catalyst being {GaH₃}_(n), wherein n is 1, 2, or 3;     -   the hydride catalyst being {GaH₃};     -   the hydride catalyst being {GaH₃}₂;     -   the hydride catalyst being {GaH₃}₃;     -   the hydride catalyst being GaH₃(L), wherein L is NR₃, with each         R independently C_(m)H_(2m+1) and m=1-10;     -   the hydride catalyst being GaH₃(L), wherein L is a substituted         ethylenediamine;     -   the hydride catalyst being GaH₃(L), wherein L is         N,N,N′,N′-tetramethyl-ethylenediamine;     -   the hydride catalyst being GaH₃(L), wherein L is         N,N,N′,N′-tetramethyl-propanediamine;     -   the hydride catalyst comprising two elements from Group I, II,         or III of the Periodic Table;     -   the hydride catalyst being selected from the group consisting of         LiAlH₄, LiAlH_(n)R_(4−n), NaAlH_(n)R_(4−n), KAlH_(n)R_(4−n),         RbAlH_(n)R_(4−n), CsAlH_(n)R_(4−n), and combinations thereof,         wherein n=1, 2, or 3 and each R is independently C_(m)H_(2m+1)         with m=1-10 or an aliphatic group having an oxygen or nitrogen         atom;     -   the hydride catalyst being LiAlH₄;     -   the hydride catalyst being LiAlH_(n)R_(4−n), wherein n=1, 2, or         3 and each R is independently C_(m)H_(2m+1) with m=1-10 or an         aliphatic group having an oxygen or nitrogen atom;     -   the hydride catalyst being selected from the group consisting of         NaAlH_(n)R_(4−n), wherein n=1, 2, or 3 and each R is         independently C_(m)H_(2m+1) with m=1-10 or an aliphatic group         having an oxygen or nitrogen atom;     -   the hydride catalyst being selected from the group consisting of         KAlH_(n)R_(4−n), wherein n=1, 2, or 3 and each R is         independently C_(m)H_(2m+1) with m=1-10 or an aliphatic group         having an oxygen or nitrogen atom;     -   the hydride catalyst being selected from the group consisting of         RbAlH_(n)R_(4−n), wherein n=1, 2, or 3 and each R is         independently C_(m)H_(2m+1) with m=1-10 or an aliphatic group         having an oxygen or nitrogen atom;     -   the hydride catalyst being selected from the group consisting of         CsAlH_(n)R_(4−n), wherein n=1, 2, or 3 and each R is         independently C_(m)H_(2m+1) with m=1-10 or an aliphatic group         having an oxygen or nitrogen atom;     -   the aliphatic group having an oxygen or nitrogen atom being         selected from the group consisting of —CH₂OMe, —CH₂CH₂OMe,         —OCH₂CH₂CH₂OMe, —CH₂CH₂NMe₂, an aromatic group, and combinations         thereof;     -   the heterogeneous catalyst being sodium         bis(2-methoxyethoxy)aluminum hydride [Na(—O(Me)—C₂H₄—O—)₂AlH₂];     -   the aromatic group being phenyl or substituted phenyl;     -   the heterogeneous catalyst being a silylamide catalyst;     -   the silylamide catalyst having the formula M[N(SiR₃)₂]_(x),         wherein x=1 when M is Li, Na, or K; x=2 when M=Mg, Ca, Sr, or         Ba; x=3 when M=Al or Ga; and each R is independently         C_(m)H_(2m+1) with m=1-10 or an aromatic group;     -   the silylamide catalyst having the formula Li[N(SiR₃)₂], wherein         each R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silylamide catalyst having the formula Na[N(SiR₃)₂], wherein         each R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silylamide catalyst having the formula Na[N(SiR₃)₂], wherein         each R is independently C_(m)H_(2m+1) with m=1-4;     -   the silylamide catalyst being sodium bis(trimethylsilyl)amide;     -   the silylamide catalyst having the formula K[N(SiR₃)₂], wherein         each R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silylamide catalyst having the formula K[N(SiR₃)₂], wherein         each R is independently C_(m)H_(2m+1) with m=1-4;     -   the silylamide catalyst being potassium         bis(trimethylsilyl)amide;     -   the silylamide catalyst having the formula Mg[N(SiR₃)₂]₂,         wherein each R is independently C_(m)H_(2m+1) with m=1-10 or an         aromatic group;     -   the silylamide catalyst having the formula Ca[N(SiR₃)₂]₂,         wherein each R is independently C_(m)H_(2m+1) with m=1-10 or an         aromatic group;     -   the silylamide catalyst having the formula Sr[N(SiR₃)₂]₂,         wherein each R is independently C_(m)H_(2m+1) with m=1-10 or an         aromatic group;     -   the silylamide catalyst having the formula Ba[N(SiR₃)₂]₂,         wherein each R is independently C_(m)H_(2m+1) with m=1-10 or an         aromatic group;     -   the silylamide catalyst having the formula Al[N(SiR₃)₂]₃,         wherein each R is independently C_(m)H_(2m+1) with m=1-10 or an         aromatic group;     -   the silylamide catalyst having the formula Ga[N(SiR₃)₂]₃,         wherein each R is independently C_(m)H_(2m+1) with m=1-10 or an         aromatic group;     -   the heterogeneous catalyst being a silanide catalyst;     -   the silanide catalyst having the formula         Na[Al(SiH₃)(Si₂H₅)(OCH₂CH₂OMe)₂];     -   the silanide catalyst having the formula M(Si_(n)H_(2n−1))_(x)         or M(SiR₃)_(x), wherein n=1-4 and x=1 when M is Li, Na, K, Rb,         or Cs; x=2 when M=Mg, Ca, Sr, or Ba; x=3 when M=Al or Ga; and         each R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula M(Si_(n)H_(2n−1))_(x),         wherein n=1-4 and x=1 when M is Li, Na, K, Rb, or Cs; x=2 when         M=Mg, Ca, Sr, or Ba; and x=3 when M=Al or Ga;     -   the silanide catalyst having the formula LiSiH₃;     -   the silanide catalyst having the formula NaSiH₃;     -   the silanide catalyst having the formula KSiH₃;     -   the silanide catalyst having the formula RbSiH₃;     -   the silanide catalyst having the formula CsSiH₃;     -   the metal silanide catalyst having the formula LiSiPh₃;     -   the metal silanide catalyst having the formula NaSiPh₃;     -   the metal silanide catalyst having the formula KSiPh₃;     -   the metal silanide catalyst having the formula RbSiPh₃;     -   the metal silanide catalyst having the formula CsSiPh₃;     -   the silanide catalyst having the formula LiSi₂H₅;     -   the silanide catalyst having the formula NaSi₂H₅;     -   the silanide catalyst having the formula KSi₂H₅;     -   the silanide catalyst having the formula RbSi₂H₅;     -   the silanide catalyst having the formula CsSi₂H₅;     -   the silanide catalyst having the formula Mg(SiH₃)₂,     -   the silanide catalyst having the formula Ca(SiH₃)₂,     -   the silanide catalyst having the formula Sr(SiH₃)₂,     -   the silanide catalyst having the formula Ba(SiH₃)₂,     -   the silanide catalyst having the formula Al(SiH₃)₃,     -   the silanide catalyst having the formula Ga(SiH₃)₃;     -   the silanide catalyst having the formula M(SiR₃)_(x), wherein         x=1 when M is Li, Na, K, Rb, or Cs; x=2 when M=Mg, Ca, Sr, or         Ba; x=3 when M=Al or Ga; and each R is independently         C_(m)H_(2m+1) with m=1-10 or an aromatic group;     -   the silanide catalyst having the formula Li(SiR₃), wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula Na(SiR₃), wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula K(SiR₃), wherein each R         is independently C_(m)H_(2m+1) with m=1-10 or an aromatic group;     -   the silanide catalyst having the formula Rb(SiR₃), wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula Cs(SiR₃), wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula Mg(SiR₃)₂, wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula Ca(SiR₃)₂, wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula Sr(SiR₃)₂, wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula Ba(SiR₃)₂, wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula Al(SiR₃)₃, wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the silanide catalyst having the formula Ga(SiR₃)₃, wherein each         R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic         group;     -   the heterogeneous catalyst is on a support;     -   the catalyst being physically bound to a support;     -   the catalyst being chemically bound to a support;     -   the catalyst being both physically and chemically bound to a         support;     -   the support being alumina (Al₂O₃), silica (SiO₂), or         combinations thereof;     -   the support being alumina (Al₂O₃),     -   the support being silica (SiO₂);     -   the heterogeneous catalyst being in pellet form;     -   the heterogeneous catalyst comprising approximately 0.1% w/w to         approximately 70% w/w of the heterogeneous catalyst and support         combination;     -   the heterogeneous catalyst comprising approximately 1% w/w to         approximately 50% w/w of the heterogeneous catalyst and support         combination; and/or     -   the heterogeneous catalyst comprising approximately 1% w/w to         approximately 5% w/w of the heterogeneous catalyst and support         combination.

Si-containing film forming composition produced by any of the methods disclosed above are also disclosed. The disclosed compositions may further include one or more of the following aspects:

-   -   the Si-containing film forming composition comprising         approximately 0 ppmw to approximately 100 ppmw halide         contaminants;     -   the Si-containing film forming composition comprising         approximately 0 ppmw to approximately 25 ppmw halide         contaminants;     -   the Si-containing film forming composition comprising         approximately 0 ppmw to approximately 5 ppmw halide         contaminants;     -   the Si-containing film forming composition comprising         approximately 90% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 95% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 97% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 10% w/w i-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 5% w/w i-Si₄H₁₀; and/or     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 3% w/w i-Si₄H₁₀;

Methods of maintaining the vapor pressure of tetrasilane during vapor deposition processes are also disclosed. The vapor deposition processes use any of the Si-containing film forming composition disclosed above. The Si-containing film forming composition is maintained at a vaporizing temperature. The disclosed methods may further include one or more of the following aspects:

-   -   the Si-containing film forming composition comprising         approximately 90% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 95% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 97% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 10% w/w i-Si₄H₁₀; or     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 5% w/w i-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 3% w/w i-Si₄H₁₀;     -   the Si-containing film forming composition having an initial         vapor pressure at the vaporizing temperature;     -   the vaporizing temperature ranging from approximately 0° C. to         approximately 50° C.;     -   the vaporizing temperature ranging from approximately 20° C. to         approximately 25° C.;     -   maintaining approximately 80% of the initial vapor pressure of         the Si-containing film forming composition at the vaporizing         temperature until approximately 95% w/w of Si-containing film         forming composition is consumed; and/or     -   maintaining approximately 90% of the initial vapor pressure of         the Si-containing film forming composition at the vaporizing         temperature until approximately 95% w/w of Si-containing film         forming composition is consumed;     -   maintaining approximately 95% of the initial vapor pressure of         the Si-containing film forming composition at the vaporizing         temperature until approximately 95% w/w of Si-containing film         forming composition is consumed.

Methods of reducing the formation of branched polysilanes during polymerization are also disclosed. The polymerization processes use any of the Si-containing film forming compositions disclosed above. The disclosed methods may further include one or more of the following aspects:

-   -   the Si-containing film forming composition comprising         approximately 90% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 95% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 97% w/w to approximately 100% w/w n-Si₄H₁₀;     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 10% w/w i-Si₄H₁₀; and/or     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 5% w/w i-Si₄H₁₀; and/or     -   the Si-containing film forming composition comprising         approximately 0% w/w to approximately 3% w/w i-Si₄H₁₀.

Notation and Nomenclature

Certain abbreviations, symbols, and terms are used throughout the following description and claims, and include:

As used herein, the indefinite article “a” or “an” means one or more.

As used herein, the terms “approximately” or “about” mean ±10% of the value stated.

As used herein, the term “comprising” is inclusive or open-ended and does not exclude additional, unrecited materials or method steps; the term “consisting essentially of” limits the scope of a claim to the specified materials or steps and additional materials or steps that do not materially affect the basic and novel characteristics of the claimed invention; and the term “consisting of” excludes any additional materials or method steps not specified in the claim.

As used herein, the term “higher silanes” means Si_(a)H_(2a+2), wherein a=4-100 and the term “lower silanes” means Si_(n)H_(2n+2) with n=1-3. The higher silanes may be linear or branched.

As used herein, the term “catalyst” means a substance that increases the rate of a reaction without modifying the overall standard Gibbs energy change in the reaction. As used herein, the term “catalyst” includes substances that do not undergo any permanent chemical change as well as those that do (the latter sometimes referred to as “pre-catalysts”).

As used herein, the term “heterogeneous catalyst” means a catalyst which is present in a different phase from the reactants (e.g., a solid catalyst versus a liquid reactant; or a liquid catalyst that is not capable of being mixed with a liquid reactant). The heterogeneous catalyst may be on or blended with a support, which is intrinsically inert or less active than the catalyst.

As used herein, the term “quenching agent” means a substance that deactivates a reaction.

As used herein, the term “residence time” means the amount of time the lower silane reactant spends in the flow through reactor.

As used herein, the abbreviation “RT” means room temperature, which is a temperature ranging from approximately 18° C. to approximately 25° C.

As used herein, the term “hydrocarbyl group” refers to a functional group containing carbon and hydrogen; the term “alkyl group” refers to saturated functional groups containing exclusively carbon and hydrogen atoms. The hydrocarbyl group may be saturated or unsaturated. Either term refers to linear, branched, or cyclic groups. Examples of linear alkyl groups include without limitation, methyl groups, ethyl groups, propyl groups, butyl groups, etc. Examples of branched alkyls groups include without limitation, t-butyl. Examples of cyclic alkyl groups include without limitation, cyclopropyl groups, cyclopentyl groups, cyclohexyl groups, etc.

As used herein, the abbreviation “Me” refers to a methyl group; the abbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refers to a propyl group; the abbreviation “nPr” refers to a “normal” or linear propyl group; the abbreviation “iPr” refers to an isopropyl group; the abbreviation “Bu” refers to a butyl group; the abbreviation “nBu” refers to a “normal” or linear butyl group; the abbreviation “tBu” refers to a tert-butyl group, also known as 1,1-dimethylethyl, the abbreviation “sBu” refers to a sec-butyl group, also known as 1-methylpropyl; the abbreviation “iBu” refers to an iso-butyl group, also known as 2-methylpropyl; the term “halide” refers to the halogen anions F—, Cl—, Br—, and I—; and the abbreviation “TMS” refers to trimethylsilyl or —SiMe3.

As used herein, the term “aromatic group” refers to cyclic, planar molecules with a ring of resonance bonds that exhibit more stability than other geometric or connective arrangements with the same set of atoms. Exemplary aromatic groups include substituted or unsubstituted phenyl groups (i.e., C₆R₅, wherein each R is independently H or a hydrocarbyl group).

As used herein, the term “independently” when used in the context of describing R groups should be understood to denote that the subject R group is not only independently selected relative to other R groups bearing the same or different subscripts or superscripts, but is also independently selected relative to any additional species of that same R group. For example in the formula MR¹ _(x)(NR²R³)_((4−x)), where x is 2 or 3, the two or three R¹ groups may, but need not be identical to each other or to R² or to R³. Further, it should be understood that unless specifically stated otherwise, values of R groups are independent of each other when used in different formulas.

The standard abbreviations of the elements from the Periodic Table of elements are used herein. It should be understood that elements may be referred to by these abbreviations (e.g., Si refers to silicon, C refers to carbon, H refers to hydrogen, etc.).

As used herein, the Periodic Table refers to the tabular arrangement of chemical elements; Group I of the Periodic Table refers to H, Li, Na, K, Rb, Cs, and Fr. Group II of the Periodic Table refers to Be, Mg, Ca, Sr, Ba, and Ra. Group III of the Periodic Table refers to B, Al, Ga, In, Tl, and Nh.

Any and all ranges recited herein are inclusive of their endpoints (i.e., x=1 to 4 or x ranges from 1 to 4 includes x=1, x=4, and x=any number in between), irrespective of whether the term “inclusively” is used.

BRIEF DESCRIPTION OF THE DRAWINGS

For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawing in which reference numbers are used throughout uniformly, wherein:

FIG. 1 is a schematic diagram of a batch apparatus in which the disclosed synthesis methods may be performed;

FIG. 2 is a schematic diagram of a flow-through apparatus in which the disclosed synthesis methods may be performed;

FIG. 3 is a schematic diagram of one embodiment of the flow-through apparatus of FIG. 2;

FIG. 4 is a schematic diagram of one embodiment of the reactor of FIG. 3;

FIG. 5 is a gas chromatogram of the volatile liquid products from the dry ice trap after one pass of liquid Si₃H₈ through the Vitride™ on Silica catalyst (Example 4);

FIG. 6 is a gas chromatogram of the volatile liquid products distilled from the dry ice trap after one pass of liquid Si₃H₈ through the KN(SiMe₃)₂ catalyst (Example 8);

FIG. 7 is a graph of the n-Si₄H₁₀:i-Si₄H₁₀ ratio over time at ambient temperature; and

FIG. 8 is a graph of the n-Si₄H₁₀:i-Si₄H₁₀ ratio in a 1.2 L stainless steel bubbler over time at room temperature (triangle) or 35° C. (square).

DESCRIPTION OF PREFERRED EMBODIMENTS

Methods of selectively synthesizing n-tetrasilane are disclosed. Isomers of tetrasilane exhibit differences in boiling points. The boiling point of 80-90% n-Si₄H₁₀ is 107° C. according to the online catalog from Gelest. In contrast, the boiling point for i-Si₄H₁₀ is 101.7° C. Fehér et al., Inorg. Nucl. Chem. Lett., 1973, 9, 931.

In addition to having different vapor boiling points, the isomers may also have different evaporation behavior and thermal stability, due at least to different steric geometries shown above. These differences may create a drift in any vapor processes if one isomer enriches over time. This effect has been demonstrated with other types of isomers (see, e.g., Mehwash Zia and Muhammad Zia-ul-Haq, Journal of Contemporary Research in Chemistry (2016) 1(1): 34-41).

As a result, supplying a tetrasilane precursor consisting essentially of one isomer, enriched with one isomer, or having a fixed isomer ratio is important for having a reproducible rate of film growth per cycle in vapor deposition processes.

Similarly, polymerization using the different isomers may produce different polymerization products. In other words, iso-tetrasilane may produce a polymer having more branching than one produced by n-tetrasilane.

Applicants have discovered methods of tuning and optimizing the tetrasilane isomer ratio. The pure isomers or isomer enriched mixtures are prepared by heterogeneous catalysis of silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), or mixtures thereof. The lower silane reactants (i.e., Si_(n)H_(2n+2), with n=1-3) provide an attractive starting material due to commercial availability. Various process parameters may be adjusted to produce the desired isomer ratio. Exemplary process parameters include the relative amount of the starting compounds and catalyst selection. Temperature and reaction time for a batch process or residence time in a flow through process may also impact isomer yield. The resulting higher silane products are isomer content specific and high purity. One of ordinary skill in the art will recognize that safety protocols are required when working with these reactants and products.

Tetrasilane is synthesized by reacting a Si_(n)H_((2n+2)) reactant, wherein n=1-3, with a heterogeneous catalyst. The Si_(n)H_((2n+2)) reactant may be SiH₄, Si₂H₆, Si₃H₈, or combinations thereof. These reactants are available commercially. These reactants may be used in the disclosed processes in gaseous or liquid form or, for a mixture, as a combination. For example, the reactant may be gaseous Si₂H₆ and liquid Si₃H₈.

In the examples that follow, the Si_(n)H_((2n+2)) reactant is gaseous or liquid Si₃H₈ or a mixture of liquid Si₂H₆ and liquid Si₃H₈. The examples demonstrate that the use of liquid Si₃H₈ produces better n-Si₄H₁₀/i-Si₄H₁₀ selectivity as compared to the use of gaseous Si₃H₈. Example 4 demonstrates that a Si₂H₆/Si₃H₈ reaction mixture reduces the number of heavier polysilanes (Si≥6). As a result, synthesis of the desired polysilane may be optimized by selecting the appropriate Si_(a)H_((2a+2)) reactant. Some optional reactant combinations that will reduce the number of heavier polysilanes include between approximately 0.1% w/w to approximately 60% w/w Si₃H₈ and between approximately 40% w/w and 99.9% w/w Si₂H₆; between approximately 0.1% w/w to approximately 25% w/w Si₃H₈ and between approximately 75% w/w and 99.9% w/w Si₂H₆; or between approximately 0.1% w/w to approximately 10% w/w Si₃H₈ and between approximately 90% w/w and 99.9% w/w Si₂H₆.

The heterogeneous catalysts are selected from a Group I, II or III element from the Periodic Table or oxides, alkyls, hydrides, silanides, or silyl amides thereof, preferably from Group I and/or III, and more preferably K and/or Al, are suitable to produce the n-Si₄H₁₀:i-Si₄H₁₀ mixture having a ratio ranging from approximately 5:1 to approximately 15:1. The disclosed catalysis reactions do not require the use of a quenching agent because the heterogeneous catalysts may be separated from the reactants and products using filtration in a batch process. Alternatively, the flow through reactor may be designed having suitable residence time to permit catalytic conversion of the Si_(a)H_((2a+2)) reactant.

The heterogeneous catalyst may be a Group I, II, or III element. Exemplary catalysts include K or Na. These catalysts are commercially available or may be synthesized by methods known in the art. For example, 30-40% Na/Silica is sold under the trademark ActiveGel™ by SiGNa Chemistry, Inc.

The heterogeneous catalyst may be a metal oxide catalyst. Exemplary oxide catalyst include Na₂O or K₂O. These catalysts are commercially available or may be synthesized by methods known in the art.

The heterogeneous catalyst may be a metal alkyl catalyst MR, with R=C1-C4 hydrocarbon. Exemplary metal alkyl catalysts include BuLi. These catalysts are commercially available or may be synthesized by methods known in the art.

The heterogeneous catalyst may be a metal hydride catalyst. Exemplary metal hydrides include NaH, KH, RbH, CsH, MgH₂, CaH₂, SrH₂, BaH₂, {AlH₃}, {AlH₃}₂, {AlH₃}₃, AlH₃(L), {GaH₃}, {GaH₃}₂, {GaH₃}₃, GaH₃(L), and combinations thereof, wherein n is 1, 2, or 3 and L is NR₃, with each R independently C_(m)H_(2m+1) and m=1-10. For example, L may be a substituted ethylenediamine. Exemplary ethyelenediame-containing metal hydride catalysts include AlH₃(N,N,N′,N′-tetramethyl-ethylenediamine), AlH₃(N,N,N′,N′-tetramethyl-propanediamine), GaH₃(N,N,N′,N′-tetramethyl-ethylenediamine), and/or GaH₃(N,N,N′,N′-tetramethyl-propanediamine). These catalysts are commercially available or may be synthesized by methods known in the art.

The metal hydride catalyst may be a mixed metal hydride catalyst. Exemplary mixed metal hydride catalysts include LiAlH₄, LiAlH_(n)R_(4−n), NaAlH_(n)R_(4−n), KAlH_(n)R_(4−n), RbAlH_(n)R_(4−n), CsAlH_(n)R_(4−n), and combinations thereof, wherein n=1, 2,or 3 and each R is independently C_(m)H_(2m+1) with m=1-10, an aliphatic group having an oxygen or nitrogen atom, or an aromatic group. Exemplary aliphatic groups having an oxygen or nitrogen atom include —CH₂OMe, —CH₂CH₂OMe, —OCH₂CH₂CH₂OMe, —CH₂CH₂NMe₂, an aromatic group, and combinations thereof. Exemplary aromatic groups include phenyl and substituted phenyl. These catalysts are commercially available or may be synthesized by methods known in the art. A particularly preferred mixed metal halide catalysts is sodium bis(2-methoxyethoxy)aluminum hydride [Na(—O(Me)—C₂H₄—O—)₂AlH₂].

The heterogeneous catalyst may be a metal silylamide catalyst. The metal silylamide catalyst may have the formula M[N(SiR₃)₂]_(x), wherein x=1 when M is Li, Na, or K; x=2 when M=Mg, Ca, Sr, or Ba; x=3 when M=Al or Ga; and each R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic group, preferably with m=1-4. R may be Me, Et, nPr, iPr, nBu, iBu, tBu, Ph, MePh, or other substituted phenyls. These catalysts are commercially available or may be synthesized by methods known in the art. Particularly preferred metal silylamide catalysts include sodium bis(trimethylsilyl)amide [NaN(SiMe₃)₂] and potassium bis(trimethylsilyl)amide [KN(SiMe₃)₂]. As shown in the examples that follow, catalysis of liquid Si₃H₈ using KN(SiMe₃)₂ produces high n-Si₄H₁₀:i-Si₄H₁₀ selectivity at both room temperature and 41° C. Applicants believe that NaN(SiMe₃)₂ will produce similar results.

The heterogeneous catalyst may be a metal silanide catalyst. The metal silanide catalyst may have the formula Na[Al(SiH₃)(Si₂H₅)(OCH₂CH₂OMe)₂], M(Si_(n)H_(2n−1))_(x), or M(SiR₃)_(x), wherein n=1-4 and x=1 when M is Li, Na, K, Rb, or Cs; x=2 when M=Mg, Ca, Sr, or Ba; x=3 when M=Al or Ga; and each R is independently C_(m)H_(2m+1) with m=1-10 or an aromatic group. R may be Me, Et, nPr, iPr, nBu, iBu, tBu, Ph, MePh, or other substituted phenyls. Currently, these precursors are not commercially available and are difficult to synthesize because they are pyrophoric solids. However, based on GC and FT-IR data, Applicants believe that the metal silylamide catalysts, the metal alkyl catalyst, or Na[AlH₂(OCH₂CH₂OMe)₂] sold under the trademark Vitride™ by Vertellus Holdings LLC or Red-Al® by Sigma-Aldrich Biotechnology LP, may act as pre-catalysts and convert to metal silanide catalysts. More particularly, Applicants believe that the following reactions may occur: Si₃H₈KN(SiMe₃)₂→KSi₂H₅+H₃SiN(SiMe₃)₂; Si₃H₈+LiBu→LiSi₂H₅+H₃SiBu; or 2 Si₃H₈+Na[AlH₂(OCH₂CH₂OMe)₂]=Si₂H₆+SiH₄+Na[Al(SiH₃)(Si₂H₅)(OCH₂CH₂OMe)₂]

As a result, the solid KSi₂H₅, LiSi₂H₅, or a[Al(SiH₃)(Si₂H₅)(OCH₂CH₂OMe)₂] catalyst catalytically transforms the Si_(n)H_(2n+2) reactant to a Si_(a)H_((2a+2)) mixture, wherein a=1-6, containing the n-Si₄H₁₀:i-Si₄H₁₀ mixture having a ratio ranging from approximately 5:1 to approximately 15:1.

The heterogeneous catalyst may be a mixture of two or more catalysts. Exemplary catalyst mixtures include K and K₂O or Na and Na₂O. These catalysts are commercially available or may be synthesized by methods known in the art. For example, 12-15% Na₂O/0-3% Na/85-90% Al₂O₃ is sold under the trademark Activelsom™ by SiGNa Chemistry, Inc.

Any of the heterogeneous catalysts disclosed above may be located on a support. Exemplary supports include alumina (Al₂O₃), silica (SiO₂), or combinations thereof. One of ordinary skill in the art will recognize that the catalyst may be physically and/or chemically bound to the support. For example, the catalyst may chemically react with the —OH groups on the silica or alumina supports. Alternatively, the catalyst and support may simply be physically mixed together with no chemical reaction occurring. In another alternative, physically mixing the catalyst and support may result in both physical and chemical bonding. The heterogeneous catalyst may comprise between approximately 0.1% w/w to approximately 70% w/w of the total heterogeneous catalyst and support combination. Alternatively, the heterogeneous catalyst may comprise from approximately 1% w/w to approximately 50% w/w of the total heterogeneous catalyst and support combination.

In another alternative, the heterogeneous catalyst may be commercially supplied in pellet form.

As shown in the examples that follow, the claimed heterogeneous catalysts permit more control of the polymerization process than the prior art transition metal catalysts of Group IV (Ti, Zr, Hf), VIII (Ru), IX (Co, Rh, Ir), and X (Ni, Pd, Pt) and the Lanthanides (Nd). Additionally, unlike the prior art homogeneous catalysts, the claimed heterogeneous catalysts may also be easily separated from the reaction mixture. As a result, the reaction is easier to scale to commercial volumes and the reaction product is easier to purify to semiconductor acceptable levels (i.e., very pure).

Catalysis of the lower silane reactants (i.e., Si_(n)H_(2n+2), with n=1-3) occurs when the lower silane reactant contacts the heterogeneous catalyst. The reaction may occur in a batch reactor or flow through reactor. The lower silane reactant and catalyst may be mixed in a batch reactor to form a mixture. Depending on the reactant and catalyst, the mixture may be mixed for a time period ranging from approximately 1 hour to approximately 24 hours.

The batch reaction may be performed at a temperature ranging from approximately room temperature to approximately 53° C. Alternatively, the reaction may be performed at a temperature ranging from approximately 15° C. to approximately 50° C. In another alternative, the reaction may be performed at a temperature ranging from approximately 15° C. to approximately 30° C. One of ordinary skill in the art will recognize that the reaction temperature will vary depending upon the selected catalyst as well as the desired Si_(n)H_((2n+2)) product. As shown in Table 1 of Example 1, higher temperatures tend to produce heavier polysilanes (Si≥6). The Si_(n)H_((2n+2)) product may be filtered to remove solids, such as the catalyst and/or any solid Si_(n)H_((2n+2)) product.

In a flow reactor, the Si_(a)H_((2a+2)) reactant may flow through a reactor containing catalyst pellets or catalyst supported on glass wool. The Si_(a)H_((2a+2)) reactant may have a residence time in the reactor ranging from approximately 200 second to approximately 600 seconds. The pressure in the reactor may range from approximately 10 psig (69 kPa) to approximately 50 psig (345 kPa).

The flow reaction may be performed at a temperature ranging from approximately 15° C. to approximately 170° C. Alternatively, the reaction may be performed at a temperature ranging from approximately 15° C. to approximately 150° C. In another alternative, the reaction may be performed at a temperature ranging from approximately 15° C. to approximately 100° C. In another alternative, the reaction may be performed at a temperature ranging from approximately 15° C. to approximately 50° C. In another alternative, the reaction may be performed at a temperature ranging from approximately 20° C. to approximately 150° C. In another alternative, the reaction may be performed at a temperature ranging from approximately 50° C. to approximately 100° C. One of ordinary skill in the art will recognize that the reaction temperature will vary depending upon the selected catalyst as well as the desired Si_(n)H_((2n+2)) product. As shown in Table 1 of Example 1, higher temperatures tend to produce heavier polysilanes (Si≥6).

The catalyst transforms the lower silane reactant to a Si_(a)H_((2a+2)) mixture, wherein a=1-6. The n-Si₄H₁₀:i-Si₄H₁₀ mixture is isolated from the Si_(a)H_((2a+2)) mixture. The n-Si₄H₁₀:i-Si₄H₁₀ mixture has a ratio ranging from approximately 5:1 to approximately 15:1. The n-Si₄H₁₀:i-Si₄H₁₀ mixture is fractionally distilled to produce a Si-containing film forming composition comprising approximately 95% w/w to approximately 100% w/w n-Si₄H₁₀, preferably from approximately 98% w/w to approximately 100% w/w n-Si₄H₁₀.

One of ordinary skill in the art will recognize that the reaction rate and product yield will vary depending on whether the lower silane reactant is substituted or not. The reaction products produced by the claimed unsubstituted lower silanes (i.e., Si_(n)H_((2n+2)), with n=1-3) will differ from those produced by a substituted silane containing one or more organic groups (i.e., Si_(n)R_(x)H_((2n+2−x)), with R is an organic group and X is 1 or more). See Comparative Examples 1 and 2, which demonstrate that Ru/C and Rh/C are not active for transformation of non-substituted liquid or gaseous trisilane, respectively, even though U.S. Pat. No. 5,700,400 to Nippon Oil Co, Ltd., discloses the use of Ru and Rh catalysts.

The catalysis reaction may be performed in the presence or absence of unreactive gases, such as H₂, N₂, Ar or He. The unreactive gases may be used to maintain an inert atmosphere. The unreactive gases may also be used to dilute the reaction mixture. The unreactive gases may also be used to help maintain the flow of the reaction mixture within a desired range, for example from approximately 0.1 to approximately 1,000 mL/min, alternatively from approximately 1 to approximately 10 mL/min. Of course, the addition of these unreactive gases further requires their removal from the reaction product. Therefore, in another alternative and as demonstrated in the examples that follow, the catalysis reaction may be performed under the vapor pressure of the reactants.

FIG. 1 is a diagram of an exemplary batch process system for catalytic conversion of the lower silane reactants to the n-Si₄H₁₀:i-Si₄H₁₀ mixture having a ratio ranging from approximately 5:1 to approximately 15:1. In FIG. 1, trisilane 10 and optionally disilane 11 are used as the lower silane reactants. The catalysis may be performed under an inert atmosphere, such as N₂, a noble gas (i.e., He, Ne, Ar, Kr, Xe), or combinations thereof. Any and all air must be removed from various parts of the system (e.g., reactor 20, distillation unit 40, distillation unit 50, etc.) by applying a vacuum and/or inert gas cycles. The inert gas may also serve to pressurize the trisilane 10 and optional disilane 11 to assist in delivery of the reactants to the reactor 20. Liquid nitrogen, refrigerated ethanol, an acetone/dry ice mixture, or heat transfer agents such as monoethylene glycol (MEG) or the heat transfer fluid sold under the trademark SYLTHERM™ by Dow Corning Corp. may be used to cool various parts of the system (e.g., distillation set up 40, distillation set up 50).

The Si₃H₈ reactant 10 and optional Si₂H₆ reactant 11 are added to reactor 20 via lines 12 and 13, respectively. The reactor 20 contains the catalyst (not shown). The reactor 20 also includes a stirring mechanism (not shown), such as a paddle mixer or homogenizer. The reactor 20 may also be equipped with multiple “injection ports,” pressure gauges, diaphragm valves (not shown).

The reactor 20 and any and all components that come into contact with the trisilane 10 and optional disilane 11 reactants and any products and by-products (“contact components”) must be clean and air- and moisture-free to prevent unintended reactions and/or contamination of the tetrasilane product 45. The reactor 20 and other contact components must be free of any impurities that may react with or contaminate the silanes. The reactor 20 and other contact components must also be compatible with the trisilane 10 and optional disilane 11 reactants and products and by-products.

Exemplary reactors 20 include stainless steel canisters having low surface roughness and mirror finish. The low surface roughness and mirror finish may be obtained by mechanical polishing and/or by electropolishing. High purity may be obtained by treatments that include, but are not limited to, (a) cleaning steps using dilute acids (HF, HNO₃) or bases (KOH, NaOH); followed by (b) rinsing with high purity de-ionized water to ensure the complete removal of traces of the acid or base; followed by (c) drying the reactor 20. Completion of the deionized water (DIW) rinse (step b) may be indicated when the conductivity of the rinse water reaches 100 μS/cm, and preferably below 25 μS/cm.

The drying step may include purging with an inert gas such as He, N₂, Ar (preferably N₂ or Ar); reducing the pressure in the reactor 20 or other contact components to accelerate outgassing from the surface; heating the reactor 20 or other contact components, or any combination thereof. The drying step may comprise alternate sequences of purges, during which a certain flow of inert gas is flown through the vessel, and vacuuming steps. Alternatively, the drying step may be carried out by constantly flowing a purge gas while maintaining a low pressure in the reactor 20 or other contact components. The drying efficiency and end point may be assessed by measuring the trace H₂O level in the gas emerging from the reactor 20 or other contact component. With an inlet gas having less than 10 ppb H₂O, the outlet gas should have a moisture content ranging from approximately 0 ppm to approximately 10 ppm, preferably ranging from approximately 0 ppm to approximately 1 ppm, and more preferably ranging from approximately 0 ppb to approximately 200 ppb. During the purge steps and vacuum steps, heating the reactor 20 or other contact component is known to accelerate the drying time. Reactors 20 are typically maintained at a temperature ranging from approximately 40° C. to approximately 150° C. during drying.

Once cleaned and dried, the reactor 20 must have a total leak rate below 1×10⁻⁶ std cm³/s, preferably <1×10⁻⁸ std cm³/s.

Any gases used to prepare the system for catalysis or during the catalysis process must be of semiconductor grade (i.e. free of contaminants such as trace moisture and oxygen (<1 ppm, preferably <10 ppb), and particles (<5 particles per litre @ 0.5 μm)).

The reactor 20, the source vessels of trisilane 10 and optional disilane 11, the tetrasilane product containers, and any other contact components may also be passivated by exposure to a silylating agent such as silane, disilane, or trisilane prior to the reaction. Passivation helps minimize reaction between the lower or higher silanes and the material that has been passivated.

As shown in FIG. 1, the Si₃H₈ reactant 10 and optional Si₂H₆ reactant 11 may be mixed in line 14 before introduction into air- and moisture-free reactor 20. Alternatively, the Si₃H₈ reactant 10 and optional Si₂H₆ reactant 11 may be directly introduced into reactor 20 via lines 12 and 13 (not shown). The Si₃H₈ reactant 10 and optional Si₂H₆ reactant 11 may be added to the reactor 20 via a liquid metering pump (not shown), such as a diaphragm pump, peristaltic pump, or syringe pump.

Upon completion of the addition of the Si₃H₈ reactant 10 and optional Si₂H₆ reactant 11, the reactor 20 may be heated to a temperature ranging from approximately 25° C. to approximately 150° C. or alternatively from approximately 15° C. to approximately 100° C. The reactor 20 may be maintained at the desired temperature by a jacket (not shown). The jacket may have an inlet and outlet (not shown). Inlet and outlet may be connected to a heat exchanger/chiller (not shown) and/or pump (not shown) to provide recirculation of a heating or cooling fluid. Alternatively, the temperature of the reactor 20 may be maintained using heating tape (not shown) or a heating mantle (not shown), with the heating elements connected to a temperature controlling unit (not shown). A temperature sensor (not shown) may be used to monitor the temperature of the contents of the reactor 20.

The lower silane reactant and catalyst may be stirred for a time period ranging from approximately 0.1 hour to approximately 72 hours, alternatively from approximately 1 hour to approximately 30 hours. The mixing may be performed at approximately atmospheric pressure. The progress of the reaction may be monitored using, for example, gas chromatography. The predominant reaction products are SiH₄, Si₄H₁₀, Si₅H₁₂, etc.

Upon completion of the reaction, the reactor 20 is cooled to approximately room temperature. When the reactor 20 is jacketed, any heating fluid may be replaced with a cooling fluid to assist in cooling the reactor 20 and its contents. Liquid nitrogen, refrigerated ethanol, an acetone/dry ice mixture, or heat transfer agents may be used to cool the reactor 20. Alternatively, any heating mechanism, such as heating tape or a heating mantel, may be turned off and natural cooling may occur. Any heavier liquid non-volatile silanes 23 are filtered from the catalyst and solid reaction by-products and removed from the reactor 20 via line 22. The volatile silanes 21 are stripped from reactor 20 by pressure difference.

The volatile silanes 21 may be collected in one or more traps 30 to obtain the Si_(a)H_((2a+2)) mixture 31, wherein a=1-6. Exemplary traps 30 include a dry ice/isopropanol, dry ice/acetone, refrigerated ethanol, and/or liquid nitrogen trap. The Si_(a)H_((2a+2)) mixture 31 may be collected in one or more containers and transported to a new location prior to performance of the next process steps. Alternatively, the mixture 31 may immediately be directed to a distillation unit 40 to further isolate the reaction product from any reactants and reaction by-products. The distillation unit 40 separates the Si₄H₁₀ product 45 from the SiH₄ reaction by-product 43, the volatile Si_(n)H_(2n+2) with n≥5 reaction by-products 44, and any unreacted Si₃H₈ reactant 41 and unreacted optional Si₂H₆ reactant 42. The unreacted Si₃H₈ reactant 41 and unreacted optional Si₂H₆ reactant 42 may be recycled for use in future processes.

Once again, the Si₄H₁₀ product 45 may be transported to a new location prior to performance of the next process steps. Alternatively, the Si₄H₁₀ product 45 may be directed to a fractional distillation unit 50 to separate n-tetrasilane 51 from i-tetrasilane 52. The fractional distillation may be performed using a static column or a spinning band column. The length of the spinning band distillation column is much smaller than that of the static column and may be preferred for use in crowded facilities because it takes up less space. A static column suitable to produce approximately 90% n-tetrasilane would require between approximately 90 to approximately 120 theoretical plates and would be approximately 6 to 7 meters tall.

FIG. 2 is a diagram of the flow process for catalytic conversion of the lower silane reactants to the n-Si₄H₁₀:i-Si₄H₁₀ mixture having a ratio ranging from approximately 5:1 to approximately 15:1. The same references numbers from FIG. 1 have been used for the same components in FIG. 2. As in FIG. 1, all of the contact components of FIG. 2 must be clean and air- and moisture-free. As in FIG. 1, the catalysis of FIG. 2 may be performed under an inert atmosphere, such as N₂, a noble gas (i.e., He, Ne, Ar, Kr, Xe), or combinations thereof.

Trisilane 10 and optionally disilane 11 are added to flow reactor 25 via lines 12 and 13, respectively. As in FIG. 1, the Si₃H₈ reactant 10 and optional Si₂H₆ reactant 11 may be mixed in line 14 before introduction into flow reactor 25. Alternatively, the Si₃H₈ reactant 10 and optional Si₂H₆ reactant 11 may be directly introduced into flow reactor 25 via lines 12 and 13 (not shown). The Si₃H₈ reactant 10 and optional Si₂H₆ reactant 11 may be added to the flow reactor 25 via a liquid metering pump (not shown), such as a diaphragm pump, peristaltic pump, or syringe pump. Preferably, the mixing is performed under an inert atmosphere at approximately atmospheric pressure.

As will be provided in further detail in discuss of FIG. 4 below, the catalyst (not shown) is located within the flow reactor 25. The flow reactor 25 is maintained at a temperature ranging from approximately 25° C. to approximately 250° C., alternatively from approximately 40° C. to approximately 250° C. or, in another alternative, from approximately 50° C. to approximately 100° C. The temperature selected will depend upon the catalyst selected, as well as the target reaction products. The flow reactor 25 is maintained at a pressure ranging from approximately 0.1 atm to approximately 10 atm. The flow of the trisilane 10 and optionally disilane 11 reactants is selected to provide approximately 0.01 to approximately 100 minutes of residence time in flow reactor 25, alternatively between approximately 2 minutes to approximately 20 minutes residence time, alternatively between approximately 1 second to approximately 1,000 seconds or, in another alternative, from approximately 100 seconds to approximately 600 seconds.

The Si_(a)H_((2a+2)) mixture 26, wherein a=1-6, is collected in a receiver 35 after passing the flow reactor 25. The receiver 35 may be any sort of trap, including but not limited to dry ice/isopropanol, dry ice/acetone, refrigerated ethanol, and/or liquid nitrogen traps.

As in FIG. 1 above, the Si_(a)H_((2a+2)) mixture 31 may be collected in one or more containers and transported to a new location prior to performance of the next process steps. Alternatively, the mixture 31 may immediately be directed to a distillation unit 40 to further isolate the reaction product from any reactants and reaction by-products. The distillation unit 40 separates the Si₄H₁₀ product 45 from the SiH₄ reaction by-product 43, the volatile Si_(n)H_(2n+2) with n≥5 reaction by-products 44, and any unreacted Si₃H₈ reactant 41 and optional Si₂H₆ reactant 42. The unreacted Si₃H₈ reactant 41 and unreacted optional Si₂H₆ reactant 42 may be recycled. Real time analysis and purification of the unreacted Si₃H₈ reactant 41 and unreacted optional Si₂H₆ reactant 42 may be provided to maintain quality during this continuous synthesis process, such as filters and/or in-situ GC analysis.

Once again, the Si₄H₁₀ product 45 may be transported to a new location prior to performance of the next process steps. Alternatively, the Si₄H₁₀ product 45 may be directed to a fractional distillation unit 50 to separate n-tetrasilane 51 from i-tetrasilane 52. The fractional distillation may be formed with a static column or a spinning band column. The spinning band distillation column length is much smaller than that of the static column and may be preferred for use in crowded facilities because it takes up less space. A static column suitable to produce approximately 90% n-tetrasilane would require between approximately 90 to approximately 120 theoretical plates and would be approximately 6 to 7 meters tall.

FIG. 3 is a diagram of the flow reactor 20 of FIG. 2. Please note that valves have not been included in this figure to make the figure easier to read.

The Si_(n)H_((2n+2)) reactant 100 is pressurized with nitrogen in order to supply the Si_(n)H_((2n+2)) reactant to the flow reactor 120 via line 102. Line 102 is also connected to vacuum 110. A flow regulator 101 controls the flow of the Si_(n)H_((2n+2)) reactant. The flow regulator 101 may be a graduated needle valve, electronic flow meter, etc. A gauge 103 a measures the pressure and may communicate with the flow regulator 101 to adjust accordingly.

Flow reactor 120 includes two thermocouples 121 and 122. More or fewer may be used without departing from the teachings herein. Exemplary thermocouples suitable for use in the teaching herein include Type K or Type J thermocouples.

The Si_(a)H_((2a+2)) reaction mixture exits the flow reactor 120 via line 123. Pressure regulator 104 sets the pressure in the reactor 120 and provides the pressure differential that moves the Si_(a)H_((2a+2)) reaction mixture from the flow reactor 120 to the dry ice/isopropanol trap 130. Gauge 103 b indicates pressure in the reactor 120. The dry ice/isopropanol trap 130 captures any Si_(a)H_((2a+2)) reaction products that condense above approximately −78° C.

Any volatile Si_(a)H_((2a+2)) reaction mixture that is not captured in the dry ice/isopropanol trap is condensed via line 131 to a liquid nitrogen trap 140. The liquid nitrogen trap 140 captures any Si_(a)H_((2a+2)) reaction products that condense between approximately −78° C. and approximately −196° C. Line 131 is also connected to vacuum line 110. Pressure gauge 103 c indicates pressure in line 131. SiH₄ by-product is sent to an exhaust scrubber (not shown) via line 150. N₂ 105 is used to dilute the SiH₄ by-product on its way to the exhaust scrubber. Check valve 106 prevents backflow of this pyrophoric by-product.

FIG. 4 is a diagram of the flow reactor 120 of FIG. 3. In FIG. 4, valves 201 permit the stainless steel tube flow reactor 220 to be accessed for troubleshooting or preventative maintenance. The stainless steel tube flow reactor 220 includes two thermocouples 221 and 222. As in FIG. 3, more or fewer thermocouples may be used without departing from the teachings herein. Glass wool 202 is located at the beginning and the end of the stainless steel tube flow reactor 220. The catalyst (not shown) may be packed between the glass wool 202 located at the beginning and end of the reactor or located on glass wool (not shown) packed between the glass wool 202 at the beginning and end of the flow reactor 220. As a result, the Si_(n)H_((2n+2)) reactant may be heated prior to catalysis when it passes through the glass wool at the beginning of the flow reactor 220. One of ordinary skill in the art will recognize that a layer of glass beads and pellet catalysts may be used in place of the glass wool/catalyst mixture.

When necessary, heating tape 203 provides heat to the stainless steel tube flow reactor 220. Thermal insulation 204 helps to maintain the temperature of the stainless steel tube flow reactor 220. One of ordinary skill in the art will recognize that alternative heating means may also be used without departing from the teachings herein. For example, the stainless steel tube flow reactor 220 may alternatively be placed in an oven (not shown). In that embodiment, thermal insulation 204 would not be needed.

One of ordinary skill in the art will recognize the sources for the equipment components of the systems used to practice the disclosed methods. Some level of customization of the components may be required based upon the desired temperature range, pressure range, local regulations, etc. Exemplary equipment suppliers include Parr Instrument Company equipment and components made from stainless steel.

As shown in the examples that follow, catalytic transformation of Si₃H₈ alone or mixtures of Si₃H₈ and Si₂H₆ leads to formation of tetra-, penta- and higher silanes. Tetrasilane obtained also presents as a mixture of n-Si₄H₁₀ and i-Si₄H₁₀ with ˜6-15:1 ratio, preferably from ˜8-15:1.

Fractional distillation of the n-Si₄H₁₀:i-Si₄H₁₀ mixture (50 in FIGS. 1 and 2) produces a Si-containing film forming composition comprising between approximately 90% w/w to approximately 100% w/w n-Si₄H₁₀, preferably between approximately 95% w/w to approximately 100% w/w n-Si₄H₁₀, and more preferably between approximately 97% w/w to approximately 100% w/w n-Si₄H₁₀. The Si-containing film forming compositions further comprises between approximately 0% w/w to approximately 10% w/w i-Si₄H₁₀, preferably between approximately 0% w/w to approximately 5% w/w i-Si₄H₁₀, and more preferably between approximately 0% w/w to approximately 3% w/w i-Si₄H₁₀. For example, after fractional distillation of approximately 192 grams of a 3:1 n-Si₄H₁₀:i-Si₄H₁₀ mixture using a 1 cm diameter and 100 cm long spinning band distillation column, Applicants have been able to produce approximately 90% w/w to approximately 95% w/w n-tetrasilane. One of ordinary skill in the art will recognize that higher purity n-tetrasilane would be obtained from mixtures having higher n-Si₄H₁₀:i-Si₄H₁₀ ratio and/or larger distillation columns.

The Si-containing film forming composition has a purity ranging from approximately 97% mol/mol to approximately 100% mol/mol, preferably from approximately 99% mol/mol to approximately 100% mol/mol, more preferably from approximately 99.5% mol/mol to approximately 100% mol/mol, and even more preferably from approximately 99.97% mol/mol to approximately 100% mol/mol.

The Si-containing film forming compositions preferably comprise between the detection limit and 100 ppbw of each potential metal contaminant (e.g., at least Ag, Al, Au, Ca, Cr, Cu, Fe, Mg, Mo, Ni, K, Na, Sb, Ti, Zn, etc.).

The concentration of X (wherein X=Cl, Br, or I) in the Si-containing film forming compositions may range from approximately 0 ppmw to approximately 100 ppmw, and more preferably from approximately 0 ppmw and to approximately 10 ppmw.

As shown in the examples below, the purified product may be analyzed by gas chromatography mass spectrometry (GCMS). The structure of the product may be confirmed by ¹H and/or ²⁹Si NMR.

As discussed in detail above and illustrated in the examples that follow, the Si-containing film forming composition must be stored in a clean dry storage vessel with which it does not react in order to maintain its purity.

The advantages of the disclosed synthesis methods are as follows:

-   -   Lower process temperature and higher yield of tetrasilane and         higher silanes compared to pyrolysis process, which helps reduce         cost and product isolation issues;     -   Application of heterogeneous catalysts essentially eliminates         the issues with the contamination of reaction products with the         catalyst, and eliminates steps of purification of the reaction         products from the residual catalyst;     -   Application of heterogeneous catalysts allows better control of         the reaction time, while the reported homogeneous catalysts         continue polymerizing trisilane until quenched, mostly in the         non-controlled fashion;     -   The process is solventless;     -   Purification only by distillation;     -   The waste generation is minimal and environmentally benign; and     -   Many of the starting materials are inexpensive and readily         available.

All of the above are advantageous from the standpoint of developing a scalable industrial process. As a result, the reaction product maintains purity levels suitable for the semiconductor industry without the use of stabilizers, such as toxic organic amines which may be needed to quench reactions using homogeneous catalysts.

Also disclosed are methods of using the disclosed Si-containing film forming compositions for vapor deposition methods. The disclosed methods provide for the use of the Si-containing film forming compositions for deposition of silicon-containing films, such as an elemental silicon film for fabrication of electronic or optoelectronic devices or circuits. The disclosed methods may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel type devices. The method includes: introducing the vapor of the disclosed Si-containing film forming compositions into a reactor having a substrate disposed therein and depositing at least part of the disclosed Si-containing film forming composition onto the substrate via a deposition process to form a Si-containing layer.

The disclosed methods also provide for forming a bimetal-containing layer on a substrate using a vapor deposition process and, more particularly, for deposition of SiMO_(x) or SiMN_(x) films, wherein x may be 0-4 and M is Ta, Nb, V, Hf, Zr, Ti, Al, B, C, P, As, Ge, lanthanides (such as Er), or combinations thereof.

The disclosed methods of forming silicon-containing layers on substrates may be useful in the manufacture of semiconductor, photovoltaic, LCD-TFT, or flat panel type devices. The disclosed Si-containing film forming compositions may deposit Si-containing films using any vapor deposition methods known in the art. Examples of suitable vapor deposition methods include chemical vapor deposition (CVD) or atomic layer deposition (ALD). Exemplary CVD methods include thermal CVD, plasma enhanced CVD (PECVD), pulsed CVD (PCVD), low pressure CVD (LPCVD), sub-atmospheric CVD (SACVD), atmospheric pressure CVD (APCVD), flowable CVD (f-CVD), metal organic chemical vapor deposition (MOCVD), hot-wire CVD (HWCVD, also known as cat-CVD, in which a hot wire serves as an energy source for the deposition process), radicals incorporated CVD, and combinations thereof. Exemplary ALD methods include thermal ALD, plasma enhanced ALD (PEALD), spatial isolation ALD, hot-wire ALD (HWALD), radicals incorporated ALD, and combinations thereof. Super critical fluid deposition may also be used. Among these, thermal CVD deposition is preferred for a process in which a high deposition rate, excellent film uniformity, and conformal film quality are required. Thermal ALD deposition is preferred for a process that forms a film having the high uniformity under severe conditions (e.g., trenches, holes, or vias). In one alternative, a PECVD deposition is preferred, particularly when fast growth, conformality, process-orientation and one direction films are required. In another alternative, a PEALD deposition process is preferred, particularly when superior conformality of films deposited on challenging surfaces (e.g., trenches, holes, and vias) is required.

The vapor of the Si-containing film forming composition is introduced into a reaction chamber containing a substrate. The temperature and the pressure within the reaction chamber and the temperature of the substrate are held at conditions suitable for vapor deposition of at least part of the Si-containing film forming compositions onto the substrate. In other words, after introduction of the vaporized composition into the chamber, conditions within the chamber are such that at least part of the vaporized precursor deposits onto the substrate to form the silicon-containing film. A co-reactant may also be used to help in formation of the Si-containing layer.

The reaction chamber may be any enclosure or chamber of a device in which deposition methods take place, such as, without limitation, a parallel-plate type reactor, a cold-wall type reactor, a hot-wall type reactor, a single-wafer reactor, a multi-wafer reactor, or other such types of deposition systems. All of these exemplary reaction chambers are capable of serving as an ALD reaction chamber. The reaction chamber may be maintained at a pressure ranging from about 0.5 mTorr to about 760 Torr. In addition, the temperature within the reaction chamber may range from about 20□ C to about 700□ C. One of ordinary skill in the art will recognize that the temperature may be optimized through mere experimentation to achieve the desired result.

The temperature of the reactor may be controlled by either controlling the temperature of the substrate holder and/or controlling the temperature of the reactor wall. Devices used to heat the substrate are known in the art. The reactor wall may be heated to a sufficient temperature to obtain the desired film at a sufficient growth rate and with desired physical state and composition. A non-limiting exemplary temperature range to which the reactor wall may be heated includes from approximately 20° C. to approximately 700° C. When a plasma deposition process is utilized, the deposition temperature may range from approximately 20° C. to approximately 550° C. Alternatively, when a thermal process is performed, the deposition temperature may range from approximately 300° C. to approximately 700° C.

Alternatively, the substrate may be heated to a sufficient temperature to obtain the desired silicon-containing film at a sufficient growth rate and with desired physical state and composition. A non-limiting exemplary temperature range to which the substrate may be heated includes from 150° C. to 700° C. Preferably, the temperature of the substrate remains less than or equal to 500° C.

The type of substrate upon which the silicon-containing film will be deposited will vary depending on the final use intended. A substrate is generally defined as the material on which a process is conducted. The substrates include, but are not limited to, any suitable substrate used in semiconductor, photovoltaic, flat panel, or LCD-TFT device manufacturing. Examples of suitable substrates include wafers, such as silicon, silica, glass, Ge, or GaAs wafers. The wafer may have one or more layers of differing materials deposited on it from a previous manufacturing step. For example, the wafers may include silicon layers (crystalline, amorphous, porous, etc.), silicon oxide layers, silicon nitride layers, silicon oxy nitride layers, carbon doped silicon oxide (SiCOH) layers, or combinations thereof. Additionally, the wafers may include copper layers, tungsten layers or metal layers (e.g. platinum, palladium, nickel, rhodium, or gold). The wafers may include barrier layers, such as manganese, manganese oxide, tantalum, tantalum nitride, etc. The layers may be planar or patterned. In some embodiments, the substrate may be coated with a patterned photoresist film. In some embodiments, the substrate may include layers of oxides which are used as dielectric materials in MIM, DRAM, or FeRam technologies (for example, ZrO₂ based materials, HfO₂ based materials, TiO₂ based materials, rare earth oxide based materials, ternary oxide based materials, etc.) or from nitride-based films (for example, TaN) that are used as electromigration barrier and adhesion layer between copper and the low-k layer. The disclosed processes may deposit the silicon-containing layer directly on the wafer or directly on one or more than one (when patterned layers form the substrate) of the layers on top of the wafer. Furthermore, one of ordinary skill in the art will recognize that the terms “film” or “layer” used herein refers to a thickness of some material laid on or spread over a surface and that the surface may be a trench or a line. Throughout the specification and claims, the wafer and any associated layers thereon are referred to as substrates. The actual substrate utilized may also depend upon the specific precursor embodiment utilized. In many instances though, the preferred substrate utilized will be selected from hydrogenated carbon, TiN, SRO, Ru, and Si type substrates, such as polysilicon or crystalline silicon substrates.

The substrate may be patterned to include vias or trenches having high aspect ratios. For example, a conformal Si-containing film, such as SiN or SiO₂, may be deposited using any ALD technique on a through silicon via (TSV) having an aspect ratio ranging from approximately 20:1 to approximately 100:1.

The Si-containing film forming compositions may be supplied neat. Alternatively, the Si-containing film forming compositions may further comprise a solvent suitable for use in vapor deposition. The solvent may be selected from, among others, C₁-C₁₆ saturated or unsaturated hydrocarbons.

For vapor deposition, the Si-containing film forming compositions are introduced into a reactor in vapor form by conventional means, such as tubing and/or flow meters. The vapor form may be produced by vaporizing the Si-containing film forming compositions through a conventional vaporization step such as direct liquid injection, direct vapor draw in the absence of a carrier gas, by bubbling a carrier gas through the liquid, or by sweeping the vapors with a carrier gas without bubbling it through the liquid. The Si-containing film forming compositions may be fed in liquid state to a vaporizer (Direct Liquid Injection) where it is vaporized and mixed with a carrier gas before it is introduced into the reactor. Alternatively, the Si-containing film forming compositions may be vaporized by passing a carrier gas into a container containing the composition or by bubbling the carrier gas into the composition. The carrier gas may include, but is not limited to, Ar, He, or N₂, and mixtures thereof. The carrier gas and composition are then introduced into the reactor as a vapor.

If necessary, the Si-containing film forming composition may be heated to a temperature that permits the Si-containing film forming composition to have a sufficient vapor pressure. The delivery device may be maintained at temperatures in the range of, for example, 0-150° C. Those skilled in the art recognize that the temperature of the delivery device may be adjusted in a known manner to control the amount of Si-containing film forming composition vaporized.

In addition to the disclosed composition, a reaction gas may also be introduced into the reactor. The reaction gas may be an oxidizing agent such as O₂; O₃; H₂O; H₂O₂, N₂O, oxygen containing radicals such as O⁻ or OH⁻; NO; NO₂; carboxylic acids such as formic acid, acetic acid, propionic acid; radical species of NO, NO₂, or the carboxylic acids; para-formaldehyde; and mixtures thereof. Preferably, the oxidizing agent is selected from the group consisting of O₂, O₃, H₂O, H₂O₂, oxygen containing radicals thereof such as O⁻ or OH⁻, and mixtures thereof. Preferably, when an ALD process is performed, the co-reactant is plasma treated oxygen, ozone, or combinations thereof. When an oxidizing gas is used, the resulting silicon containing film will also contain oxygen.

Alternatively, the reaction gas may H₂, NH₃, (SiH₃)₃N, hydridosilanes (such as SiH₄, Si₂H₆, Si₃H₈, Si₄H₁₀, Si₅H₁₀, Si₆H₁₂), chlorosilanes and chloropolysilanes (such as SiHCl₃, SiH₂Cl₂, SiH₃Cl, Si₂Cl₆, Si₂HCl₅, Si₃Cl₈), alkylsilanes (such as Me₂SiH₂, Et₂SiH₂, MeSiH₃, EtSiH₃), hydrazines (such as N₂H₄, MeHNNH₂, MeHNNHMe), organic amines (such as NMeH₂, NEtH₂, NMe₂H, NEt₂H, NMe₃, NEt₃, (SiMe₃)₂NH), diamines such as ethylene diamine, dimethylethylene diamine, tetramethylethylene diamine, pyrazoline, pyridine, B-containing molecules (such as B₂H₆, trimethylboron, triethylboron, borazine, substituted borazine, dialkylaminoboranes), alkyl metals (such as trimethylaluminum, triethylaluminum, dimethylzinc, diethylzinc), radical species thereof, or mixtures thereof. When H₂ or an inorganic Si containing gas is used, the resulting silicon containing film may be pure Si.

Alternatively, the reaction gas may be a hydrocarbon, saturated or unsaturated, linear, branched or cyclic, such as but not limited to ethylene, acetylene, propylene, isoprene, cyclohexane, cyclohexene, cyclohexadiene, pentene, pentyne, cyclopentane, butadiene, cyclobutane, terpinene, octane, octene, or combinations thereof.

The reaction gas may be treated by a plasma, in order to decompose the reaction gas into its radical form. N₂ may also be utilized as a reducing agent when treated with plasma. For instance, the plasma may be generated with a power ranging from about 50 W to about 500 W, preferably from about 100 W to about 200 W. The plasma may be generated or present within the reactor itself. Alternatively, the plasma may generally be at a location removed from the reactor, for instance, in a remotely located plasma system. One of skill in the art will recognize methods and apparatus suitable for such plasma treatment.

The desired silicon-containing film also contains another element, such as, for example and without limitation, B, P, As, Zr, Hf, Ti, Nb, V, Ta, Al, Si, or Ge.

The Si-containing film forming composition and one or more co-reactants may be introduced into the reaction chamber simultaneously (chemical vapor deposition), sequentially (atomic layer deposition), or in other combinations. For example, the vapor of the Si-containing film forming composition may be introduced in one pulse and two additional metal sources may be introduced together in a separate pulse (modified atomic layer deposition). Alternatively, the reaction chamber may already contain the co-reactant prior to introduction of the Si-containing film forming composition. The co-reactant may be passed through a plasma system localized within or remote from the reaction chamber, and decomposed to radicals. Alternatively, the Si-containing film forming composition may be introduced to the reaction chamber continuously while other precursors or reactants are introduced by pulse (pulsed-chemical vapor deposition). In another alternative, the Si-containing film forming composition and one or more co-reactants may be simultaneously sprayed from a shower head under which a susceptor holding several wafers is spun (spatial ALD).

In one non-limiting exemplary atomic layer deposition process, the vapor phase of the Si-containing film forming composition is introduced into the reaction chamber, where it is contacted with a suitable substrate. Excess composition may then be removed from the reaction chamber by purging and/or evacuating the reaction chamber. An oxygen source is introduced into the reaction chamber where it reacts with the absorbed Si-containing film forming compositions in a self-limiting manner. Any excess oxygen source is removed from the reaction chamber by purging and/or evacuating the reaction chamber. If the desired film is a silicon oxide film, this two-step process may provide the desired film thickness or may be repeated until a film having the necessary thickness has been obtained.

Alternatively, if the desired film is a silicon metal/metalloid oxide film (i.e., SiMO_(x), wherein x may be 0-4 and M is B, Zr, Hf, Ti, Nb, V, Ta, Al, Si, Ga, Ge, or combinations thereof), the two-step process above may be followed by introduction of a vapor of a metal- or metalloid-containing precursor into the reaction chamber. The metal- or metalloid-containing precursor will be selected based on the nature of the silicon metal/metalloid oxide film being deposited. After introduction into the reaction chamber, the metal- or metalloid-containing precursor is contacted with the substrate. Any excess metal- or metalloid-containing precursor is removed from the reaction chamber by purging and/or evacuating the reaction chamber. Once again, an oxygen source may be introduced into the reaction chamber to react with the metal- or metalloid-containing precursor. Excess oxygen source is removed from the reaction chamber by purging and/or evacuating the reaction chamber. If a desired film thickness has been achieved, the process may be terminated. However, if a thicker film is desired, the entire four-step process may be repeated. By alternating the provision of the Si-containing film forming composition, metal- or metalloid-containing precursor, and oxygen source, a film of desired composition and thickness can be deposited.

Additionally, by varying the number of pulses, films having a desired stoichiometric M:Si ratio may be obtained. For example, a SiMO₂ film may be obtained by having one pulse of the Si-containing film forming composition and one pulse of the metal- or metalloid-containing precursor, with each pulse being followed by a pulse of the oxygen source. However, one of ordinary skill in the art will recognize that the number of pulses required to obtain the desired film may not be identical to the stoichiometric ratio of the resulting film.

The silicon-containing films resulting from the processes discussed above may include SiO₂; SiC; SiN; SiON; SiOC; SiONC; SiBN; SiBCN; SiCN; SiMO, SiMN in which M is selected from Zr, Hf, Ti, Nb, V, Ta, Al, Ge, depending of course on the oxidation state of M. One of ordinary skill in the art will recognize that by judicial selection of the appropriate Si-containing film forming composition and co-reactants, the desired film composition may be obtained.

Upon obtaining a desired film thickness, the film may be subject to further processing, such as thermal annealing, furnace-annealing, rapid thermal annealing, UV or e-beam curing, and/or plasma gas exposure. Those skilled in the art recognize the systems and methods utilized to perform these additional processing steps. For example, the silicon-containing film may be exposed to a temperature ranging from approximately 200° C. and approximately 1000° C. for a time ranging from approximately 0.1 second to approximately 7200 seconds under an inert atmosphere, a H-containing atmosphere, a N-containing atmosphere, or combinations thereof. Most preferably, the temperature is 600° C. for less than 3600 seconds. Even more preferably, the temperature is less than 400° C. The annealing step may be performed in the same reaction chamber in which the deposition process is performed. Alternatively, the substrate may be removed from the reaction chamber, with the annealing/flash annealing process being performed in a separate apparatus. Any of the above post-treatment methods, but especially UV-curing, has been found effective to enhance the connectivity and cross linking of the film, and to reduce the H content of the film when the film is a SiN containing film. Typically, a combination of thermal annealing to <400° C. (preferably about 100° C.-300° C.) and UV curing is used to obtain the film with the highest density.

For a further understanding of the nature and objects of the present invention, reference should be made to the following detailed description, taken in conjunction with the accompanying drawing wherein:

EXAMPLES

The following non-limiting examples are provided to further illustrate embodiments of the invention. However, the examples are not intended to be all inclusive and are not intended to limit the scope of the inventions described herein.

The reaction products can be analyzed by any suitable means, such as by gas chromatography (GC) using part of the product stream or an aliquot of the product. In the following examples, GC analysis was performed on Agilent 7890A and Agilent 6890 Gas Chromatographs equipped with Thermal Conductivity Detector (TCD). The injection port was under inert (N₂ or Ar) atmosphere.

Exemplary method: Column: Rtx-1 (Cross bond Dimethyl Polysiloxane) 105 m×0.53 mm×5 μm. Detector T=250° C., Reference flow: 20 mL/min; Makeup flow: 5 mL/min; Carrier gas: 5 mL/min (Helium); Oven: 35° C., 8 min, ramp 20° C./min, 200° C., 13 min, Injector: 200° C., Splitless mode; Sample Size: 1.0 μL.

Example 1 Summary of Claimed Catalysts

Applicants have surprisingly discovered the selective catalytic activity of heterogeneous catalysts comprising the elements of Group I, II, and/or III of the Periodic Table, as summarized in the Tables 1 and 2:

TABLE 1 Activity of the claimed catalysts for converting liquid Si₃H₈ Selectivity Selectivity T i- n- Silanes ≥ n-Si₄H₁₀/ Si₅H₁₂ C/Si₅H₁₂ B/ Catalyst (h) Si₄H₁₀ Si₄H₁₀ Si₅H₁₂ A Si₅H₁₂ B Si₅H₁₂ C Si6 i-Si₄H₁₀ Si₅H₁₂ A Vitride ™ 30% 3 2.0 19.3 0.2 2.9 7.6 14.1 9.7 2.6:1:0.07 w/w/ Silica Vitride ™ 47% 20 2.6 17.7 0.4 3.3 6.1 8.0 6.9 19:1:0.12 w/w/ Silica KSiPh₃ 5 1.6 18.1 0.2 2.5 6.7 10.0 11.0 2.7:1:0.08 KN(SiMe₃)₂, 3 1.3 15.3 0.1 1.8 3.5 1.6 11.8 1.9:1:0.06 41° C.* KN(SiMe₃)₂ 22 1.3 14.3 0.1 2.2 5.3 11.6 10.7 2.4:1:0.05 KH 6 0.5 5.8 0.0 0.6 1.2 0.8 12.1 2.0:1:0.00 MgH₂ 6 2.0 7.3 0.1 0.7 0.7 0.3 3.6 1.0:1:0.14 LiAlH₄ 7 0.3 3.3 0.0 0.1 0.2 0.0 10.2 2.9:1:0 n-BuLi 1 0.6 1.6 0.1 1.1 2.8 2.5 2.5 2.6:1:0.09 ActiveGel ™ 2 0.8 5.9 0.0 1.1 2.1 2.0 7.9 1.9:1:0.00 ActiveGel ™ 21 1.5 11.2 0.0 2.5 4.1 13.4 7.3 1.6:1:0.00 Activelsom ™ 2 1.2 9.6 0.0 2.2 4.6 7.6 8.2 2.2:1:0.00 Activelsom ™ 21 1.6 14.0 0.0 2.8 5.7 12.5 8.6 2.0:1:0.00 All numbers in % w/w All reactions at RT except 3 hour KN(SiMe₃)₂, which was at 41° C. Si₃H₈ reactant = 99.8% w/w 1-5% w/w catalyst taken Mixtures of silanes filtered from heterogeneous catalysts prior to GC measurement, except for 3 hour KN(SiMe₃)₂ which is from the dry ice trap (See Example 6) Vitride ™ = Na[AlH₂(OCH₂CH₂OMe)₂] sold under the trademark Vitride ™ by Vertellus Holdings LLC or Red-Al ® by Sigma-Aldrich Biotechnology LP ActiveGel ™ = 30-40% Na/Silica sold under the trademark ActiveGel ™ by SiGNa Chemistry, Inc. Activelsom ™ = 12-15% Na₂O/0-3% Na/85-90% Al₂O₃ sold under the trademark Activelsom ™ by SiGNa Chemistry, Inc.

At the applied conditions, selectivity toward the n-Si₄H₁₀: KH>KN(SiMe₃)₂≈KSiPh₃>LiAlH₄>Vitride™/Silica>Activelsom™>ActiveGel™>MgH₂>BuLi

Activity in transformation of liquid Si₃H₈: Vitride™/Silica>KSiPh₃>KN(SiMe₃)₂≈Activelsom™>ActiveGel™>n-BuLi>MgH₂>KH>LiAlH₄.

TABLE 2 Activity of the claimed catalysts in % of reaction products in 1 pass of gaseous Si₃H₈ through the tube with the catalyst. Silanes ≥ Selectivity Catalyst T, ° C. i-Si₄H₁₀ n-Si₄H₁₀ Si₅H₁₂ Si6 n-Si₄H₁₀/i-Si₄H₁₀ Vitride ™/Silica 80 1.2 4.3 0.42 0.05 3.6 KH 250 0.7 1.6 0.35 0.08 2.3 LiAlH₄ 200 0.3 1.2 0.28 0.04 4.0 KN(SiMe₃)₂ 128 1.0 3.2 0.46 0.09 3.2 KSiPh₃ 50 0.2 0.9 0.10 0.09 3.0 MgH₂ 250 0.1 0.4 0.18 0.05 3.9 ActiveGel ™ 118 0.1 0.4 0.13 0.16 3.7 Activelsom ™ 150 0.3 1.0 0.30 0.03 3.6 Temperature range tested 50-300° C., the highest activity reported in the table. No solid formed at the reported conditions.

The n-Si₄H₁₀/i-Si₄H₁₀ Isomeric ratio is much higher for the liquid phase reactions.

Additional synthesis details are provided in the examples that follow.

Comparative Example 1 Summary of Results for Prior Art Catalysts with Liquid Si₃H₈

Catalysis of liquid Si₃H₈ using the prior art homogeneous catalysts Cp₂ZrCl₂/BuLi, Cp₂ZrCl₂/LiNMe₂, RuCl₄(p-Cymene)₂ and Ni(COD)₂ (COD=cyclooctadienyl) was performed [catalysts from Joyce Y. Corey, “Dehydrocoupling of Hydrosilanes to Polysilanes and Silicon Oligomers: A 30 Year Overview”, Advances in Organometallic Chemistry, Volume 51, 2004 Elsevier Inc.]. Catalysis of liquid Si₃H₈ using the prior art heterogeneous catalysts Ru (5%)/C and Rh (5%)/C was also performed [catalysts from “Method for Producing a Semiconductor Material”, Keizo Ikai, Masaki Minami; Mitsuo Matsuno, Nippon Oil Co., Ltd., U.S. Pat. No. 5,700,400 A, Aug. 14, 1995.]. FeCl₃ on silica and in combination with MMAO (MMAO=modified methylaluminoxane, formula [CH₃)_(0.95)(n-C₈H₁₇)_(0.05)AlO]_(n)) were also tested.

TABLE 3 Comparative test of catalysts toward the liquid trisilane. Si₄H₁₀, Catalyst (g) per Si₅H₁₂ 3-4 g Si₃H₈ Additive Time Result % Cp₂ZrCl₂ (0.32 g) BuLi 2.5M   1 min Polymer n.d. in Hexane Cp₂TiCl₂ (0.27 g) BuLi 2.5M   5 min Polymer n.d. in Hexane Cp₂ZrCl₂ (<0.01 g) LiNMe₂ 1.5 h Polymer n.d. Cp₂TiCl₂ (0.27 g) LiNMe₂ 0.5 h Polymer n.d. Cp₂ZrCl₂ (0.02 g) Tiba (Al^(i)Bu₃)   5 h No reaction similar (0.15 g) FeCl₃ (5%) on No   3 h No reaction similar Silica (0.11 g) FeCl₃ (5%) on MMAO   3 h No reaction similar Silica (0.11 g) (Fe:Al = 1:100) RuCl₄(p-Cymene)₂ No  24 h No reaction similar RuCl₄(p-Cymene)₂ MMAO12(35%)  24 h No reaction similar on silica RuCl₄(p-Cymene)₂ Al^(i)Bu₃/  24 h No reaction similar MMAO12(35%) on silica Ni(COD)₂ No  24 h No reaction similar Ru (5%)/C No  24 h No reaction similar Rh (5%)/C No  24 h No reaction similar n.d. = not detected. similar = relative amount of higher silanes after test is similar to that in trisilane before test within (±0.2%)

The CpTiCl₂ and CpZrCl₂ homogeneous catalysts polymerized trisilane to a non-volatile solid in a non-controllable fashion. As a result, these catalysts are not useful for controllable synthesis of isomerically enriched tetrasilane or liquid higher silanes.

The RuCl₄(p-Cymene)₂, Ni(COD)₂, and FeCl₃ homogeneous catalysts and Ru (5%)/C and Rh (5%)/C heterogeneous catalysts are not active for the transformation of non-substituted liquid trisilane to a higher silanes.

Comparative Example 2 Summary of Results for Prior Art Catalysts with Gaseous Si₃H₈

Si₃H₈ vapors (1.8-2.3 g) were passed through a flow reactor at a specified temperature at a 0.1 g/min flow rate. The reactor was a ¼ inch diameter by 5 inch long stainless steel tube containing 0.15 g Ru/C and 0.25 g of glass wool or 0.17 g Rh/C and 0.37 g of glass wool. Before experiments Ru/C, Rh/C and glass wool were kept at 240° C. under dynamic vacuum for 26 hours to remove the moisture. The products collected were analyzed by GC, see result in the Tables 4 and 5 below.

TABLE 4 Results of Trisilane passing through Ru (5%)/C. Liquid phase (%) Heavies ≥ T g Si₃H₈ g Liquid i- n- Si6 N (° C.) introduced recovered Si₃H₈ Si₄H₁₀ Si₄H₁₀ Si₅H₁₂ (%) Before experiment 99.7 0.07 0.1 0.03 0.010 1 102 1.88 1.84 99.6 0.09 0.2 0.04 0 2 151 1.82 1.80 99.7 0.08 0.2 0.04 0.002 3 202 1.99 1.94 99.7 0.07 0.16 0.06 0.004 4 252 2.26 2.10 99.7 0.06 0.15 0.07 0.008

TABLE 5 Results of Trisilane passing through Rh (5%)/C Liquid phase (%) Heavies ≥ T g Si₃H₈ g Liquid i- n- Si6 N (° C.) introduced recovered Si₃H₈ Si₄H₁₀ Si₄H₁₀ Si₅H₁₂ (%) Before experiment 99.6 0.07 0.14 0.03 0.011 1 100 1.79 1.77 99.3 0.13 0.26 0.125 0.005 2 150 1.99 1.99 99.6 0.06 0.12 0.04 0.003 3 200 1.83 1.82 99.6 0.06 0.14 0.03 0.04 4 252 1.89 1.9 99.5 0.07 0.16 0.08 0.01

The Ru (5%)/C and Rh (5%)/C heterogeneous catalysts are not active for the transformation of non-substituted gaseous trisilane to higher silanes.

Example 2 Liquid Si₃H₈ and Na[AlH₂(OCH₂CH₂OMe)₂] (35%) on Silica

A 35% w/w Na[AlH₂(OCH₂CH₂OMe)₂] on silica catalyst was prepared by mixing silica, pre-dried in a vacuum at 300° C., with a 65% w/w toluene solution of Na[AlH₂(OCH₂CH₂OMe)₂] (sold under the trademark Vitride™ by Vertellus Holdings LLC or Red-Al® by Sigma-Aldrich Biotechnology LP). The mixture was stirred 12 hours at room temperature. All volatiles were removed under dynamic vacuum. The remaining solid was utilized as the catalyst.

Liquid Si₃H₈ (3.1 g, 33.6 mmol) and the catalyst (0.18 g, Na[AlH₂(OCH₂CH₂OMe)₂]0.063 g, 0.32 mmol) were stirred for 3 hours at room temperature in a vial in a glove box. The stirring was stopped after 3 hours. Any solid was allowed to settle and an aliquot of the clear supernatant was collected for GC analysis. GC analysis of the clear solution revealed a mixture of Si₂—Si₈ silanes containing 44.8% Si₃H₈; 2.0% iso-Si₄H₁₀ and 19.3% n-Si₄H₁₀, 10.8% Si₅H₁₂ total and 14.1% of silanes with 6 or more silicon atoms in total.

Vitride™ on Silica transformed the liquid trisilane in the pot reaction to a mixture of silanes with excellent selectivity toward n-Si₄H₁₀ [n-Si₄H₁₀:i-Si₄H₁₀=9.7:1]. In order to illustrate the applicability of the process for industrial applications, a flow reaction was performed with gaseous and liquid trisilane.

Example 3 Gaseous Si₃H₈ and Na[AlH₂(OCH₂CH₂OMe)₂]

Si₃H₈ vapors (1.22-2.25 g, purity 99.8% w/w) were passed through a heated tube (4.7″ L×0.25″ ID) at a specified temperature at a 0.1 g/min flow rate. The reactor contained 50 wt % of the Na[AlH₂(OCH₂CH₂OMe)₂] (35% w/w) on silica catalyst prepared in Example 2 and 50 wt % glass wool. The products collected in a liquid nitrogen trap were analyzed by GC. The results are presented in Table 6.

TABLE 6 n- Gas phase Liquid phase (%) Si₄H₁₀/ Heavies ≥ g g (mmol) i- n- i- Si6 Lost T ° C. Si₃H₈ Liq. SiH₄ Si₂H₆ Si₃H₈ Si₃H₈ Si₄H₁₀ Si₄H₁₀ Si₅H₁₂ Si₄H₁₀ (%) (g) 55 2.28 2.23 1.15 1.05 0.58 94.3 1.4 3.8 0.41 2.7 0.039 0.05 80 2.06 2.07 0.47 0.37 0.58 94.0 1.2 4.3 0.42 3.6 0.045 −0.01 104 2.35 2.35 0.48 0.31 0.58 94.9 0.9 3.8 0.31 4.2 0.033 0 131 2.26 2.27 0.52 0.22 0.58 96.4 0.7 2.7 0.19 3.9 0.020 −0.01 162 2.49 2.49 0.54 0.12 0.58 97.9 0.5 1.4 0.12 2.8 0.020 0 The “g Si₃H₈” column is the amount of gaseous Si₃H₈ introduced into the reactor. The “g. liq.” column is the amount of liquid recovered. The “gas phase (mmol)” columns was the mmol of silanes in 50 cm³ of receiver at 20° C. calculated using the gas law, known pressure of trisilane at 20° C. over liquid Trisilane, and relative intensities of SiH₄, Si₂H₆, and Si₃H₈ in the GC of the gas phase. The “Si₅H₁₂” column is the total relative amount of pentasilane. The “heavies ≥ Si₆” column is the total relative amount of silanes having 6 or more silicon atoms and visible on GC chromatogram. The “lost (g)” column is a lost weight parameter indicative for solid polymer formation in the reactor. If lost weight is close to 0 in the individual experiment, polymer formation is not taking place.

As in Example 2, the Vitride™ on Silica catalyst showed significant activity toward gaseous trisilane.

Comparatively, the relative amount of heavy silanes with 6 or more silicon atom is lower in the gaseous reaction than in the liquid reaction according to GC. In addition, no solid polymeric silanes formed in the gas flow process.

However the selectivity of the gaseous process toward the n-tetrasilane is low.

In order to illustrate that the selectivity and the relative amount of heavy silanes might be tuned, liquid trisilane passed through the flow reactor with Vitride™ on Silica, see the next example.

Example 4 Liquid Si₃H₈ and Na[AlH₂(OCH₂CH₂OMe)₂], Flow Process

Three separate samples of liquid Si₃H₈ passed through the same reactor (20.9 cm L×1 cm ID) at 52.0±0.7° C. and pressure 31.1±0.6 psig with the flow 1.1±0.1 g/min. The reactor contained 7.9 g of 46.8% w/w Vitride™ on silica (3.7 g of active component) on 3.0 g of glass wool. The effluent was collected in the dry ice trap, followed by liquid nitrogen trap. The content of the traps was analyzed by GC. The content of dry ice trap was distilled, affording 4.4 g of nondistilled liquid. The non-distilled liquid was a mixture of silanes with 6 and more silicon atoms [GC]. The distillate is a mixture of volatile silanes with 1-8 silicon atoms. FIG. 5 is a gas chromatogram of the volatile liquid products from the dry ice trap after one pass of liquid Si₃H₈ through the Vitride™ on Silica catalyst. The results are summarized in the Tables 7 and 8 below.

TABLE 7 Results of flow reaction using liquid trisilane and Vitride ™ on Silica. Si₃H₈ Selectivity: n- Residence Precursor consumed Si₄H₁₀:i- Yield: n- Yield: Av. T time content (g) (g) Si₄H₁₀ Si₄H₁₀ % Si₅H₁₂ % (° C.) (Seconds) (149.5 g) 77.0 6.3:1 13.6 6.3 52.0 ± 0.7 275-421 [99.7% Av. = 358 Si₃H₈] (163.8 g) 44.1* 7.2:1 10.5 2.3 50.7 ± 1.1 271-418 [99.7% Av. = 369 Si₃H₈] (143.9 g) 38.2 7.2:1 10.2 2.5 53.7 ± 2.3 210-432 [99.6% Av. = 359 Si₃H₈]

TABLE 8 Mass balance, Yield in g/mol. Yield of Products g (precursor Volatile mixture)/ Si₅H₁₂ Heavies ≥ Non Precursor Mol SiH₄ Si₂H₆ i-Si₄H₁₀ n-Si₄H₁₀ (total) Si6 volatile 99.7% 149.5 g 7.1 g, 26.0 g, 3.44 g, 20.19 g, 9.35 g, 1.52 g 4.4 g Si₃H₈ Si₃H₈— 0.22 mol 0.42 mol 0.03 mol 0.16 mol 0.06 mol 1.615 mol Normalized 13.69% 29.14% 1.96% 11.50% 4.27% — — to 100% Si₃H₈ in mol 99.6% 143.9 g 2.56 g, 15.85 g, 2.04 g, 15.15 g, 3.62 g, 0.79 g 0.7 g Si₃H₈ Si₃H₈— 0.08 mol 0.25 mol 0.02 mol 0.12 mol 0.02 mol 1.553 mol Normalized  5.13% 13.22% 0.86%  6.42% 1.23% — — to 100% Si₃H₈ in mol 1. Similar catalyst used in all experiments, 1 and 14 days after packing. 2. Vitride ™ on Silica is significantly active. 3. 159 g of Si₃H₈ consumed by 7.9 g of 46.8% Vitride ™ on silica (3.7 g of active component) in 3 experiments (1 pass each, results of 2 experiments shown here) producing n-Si₄H₁₀ with reasonable selectivity and 10-14% yield. 4. The present example illustrates a potential for scaling.

Example 5 Liquid Si₂H₆/Si₃H₈ Mixture and Na[AlH₂(OCH₂CH₂OMe)₂], Flow Process

Liquid Si₂H₆ (42.5% w/w) —Si₃H₈ (57.5% w/w) (174.0 g) passed through the reactor (20.9 cm L×1 cm ID) at 51.9±3.5° C. and pressure 30.6±0.4 psig with the flow 1.4±0.3 g/min, corresponding to the residence time 442±77 sec. The reactor contained 7.0 g of 46.8% w/w Vitride™ on silica (3.3 g of active component) on 2.6 g of glass wool. The effluent was collected in the dry ice trap, followed by liquid nitrogen trap. The content of the traps was analyzed by GC. The content of dry ice trap was distilled, affording 2.0 g of nondistilled liquid. The non-distilled liquid was a mixture of silanes with 6 and more silicon atoms [GC]. The distillate is a mixture of volatile silanes with 1-8 silicon atoms. The results are summarized in the Tables 9 and 10 below.

TABLE 9 Results of flow reaction using disilane-trisilane mixture and Vitride ™ on Silica. Si₂H₆ Si₃H₈ Selectivity: Volatile Precursor formed consumed n-Si₄H₁₀:i- Yield: Yield: Heavies ≥ Non content (g) (g) (g) Si₄H₁₀ n-Si₄H₁₀ % n-Si₅H₁₂ % Si6 volatile 100.05 g Si₃H₈ +29.0 −52.67 5.5:1 9.9 2.6 0.31 g 2.0 g (57.5%) & 73.95 g Si₂H₆ (42.5%)

TABLE 10 Comparison of products for passing of Si₃H₈ and Si₂H₆—Si₃H₈ mixture Yield of Products Volatile g (precursor i- n- Si₅H₁₂ Heavies ≥ Non mixture)/Mol SiH₄ Si₂H₆ Si₄H₁₀ Si₄H₁₀ (total) Si6 volatile Si₃H₈: 149.5 g 4.75 g 17.39 g 2.30 g 13.51 g 6.25 g 1.02 g 2.94 g Si₃H₈—1.615 mol Normalized to 100 g Si₃H₈ Si₂H₆—Si₃H₈: 174 g,  8.0 g 28.99 g 1.82 g  9.88 g 2.60 g 0.31 g 2.00 g Si₃H₈: 100.05 g, 1.08 mol Normalized to 100 g Si₃H₈

As seen from tables, relative amount of heavier silanes (Si≥6) is lower for the mixture of Si₂H₆—Si₃H₈.

Example 6 Si₃H₈ and KN(SiMe₃)₂

Liquid Si₃H₈ (28.8 g, purity 99.8% w/w) and solid KN(SiMe₃)₂ (0.3 g, 1.5 mmol) were charged into a reactor equipped with a thermocouple in a glove box. Two traps were installed after the reactor. The first trap after the condenser remains empty at room temperature during the reaction. The second trap is cooled with liquid nitrogen to trap SiH₄ and Si₂H₆ during the reaction. The reactor was connected to a manifold and the N₂ atmosphere replaced with a He atmosphere. The condenser was filled with dry ice. The reaction mixture under 1 atm. of helium was heated to 41-50° C. and stirred for 3 hours. After 3 hours, the heating was stopped and the reaction mixture cooled to room temperature. Dry ice was removed from the condenser. The first trap was cooled with dry ice and the second trap remained cooled with liquid N₂. The reaction products were stripped under dynamic vacuum in the dry ice trap [20.2 g of liquid, GC: 74.2% Si₃H₈; 1.3% iso-Si₄H₁₀ and 15.3% n-Si₄H₁₀] and liquid nitrogen trap [4.7 g, GC: 45.9% SiH₄, 49.1% Si₂H₆, 5.0% Si₃H₈]. Undistilled reaction product [3.2 g] remaining in the pot was filtered and also analyzed by GC [mixture of Si₅-Si₁₂ silanes].

KN(SiMe₃)₂ transformed the liquid trisilane in the pot reaction to a mixture of silanes with excellent selectivity toward the n-Si₄H₁₀[n-Si₄H₁₀:i-Si₄H₁₀=11.8:1]. In order to illustrate the applicability of the process for industrial applications, flow reaction was performed with gaseous and liquid trisilane.

Example 7 Gaseous Si₃H₈ and KN(SiMe₃)₂

Experiments were conducted on the similar setup as in Example 3. The results of the experiments are provided in Table 11. The flow reactions were performed at different temperatures to check the performance of catalyst.

TABLE 11 Results of gaseous Trisilane passing through KN(SiMe₃)₂. Gas phase Liquid phase (%) n- T g g (mmol) i- n- Si₄H₁₀/ Heavies ≥ Lost (° C.) Si₃H₈ Liq SiH₄ Si₂H₆ Si₃H₈ Si₃H₈ Si₄H₁₀ Si₄H₁₀ Si₅H₁₂ i-Si₄H₁₀ Si₆ (%) (g) 42 2.4 2.4 0.79 0.09 0.58 98.4 0.2 0.9 0.15 4.5 0.33 0 63 1.68 1.55 0.15 0.05 0.59 98.5 0.3 1.0 0.12 3.3 0.15 0.07 95 1.83 1.66 0.36 0.11 0.59 98.0 0.4 1.3 0.12 3.3 0.20 0.11 128 1.89 1.71 2.10 0.57 0.59 95.2 1.0 3.2 0.46 3.2 0.09 0.12 128 2.07 1.97 0.73 0.21 0.58 97.2 0.6 1.9 0.21 3.2 0.15 0.04 161 1.88 1.69 1.98 0.58 0.59 95.2 1.2 3.1 0.46 2.6 0.07 0.13 196 2.01 1.83 3.68 0.95 0.59 94.9 1.4 3.1 0.47 2.2 0.07 0.12

The catalytic activity increases with an increase of temperature. At the same time, the selectivity toward n-Si₄H₁₀ decreases with the increase of temperature.

The relative amount of non-volatile silanes remaining in the tube with the catalyst increases with the increase of temperature, being low at 63° C. and 42° C.

In order to illustrate that the selectivity and the relative amount of heavy silanes might be tuned in the flow process, the liquid trisilane passed through the flow reactor with KN(SiMe₃)₂ at ˜80° C., see the next example.

Example 8 Flow Process with Liquid Si₃H₈ and Solid KN(SiMe₃)₂ Catalyst

Si₃H₈ liquid (178.2 g) passed through the reactor at 73.2±1.8° C. and pressure 27.2±0.5 psig with the flow 1.2±0.3 g/min, corresponding to the residence time 467±106 sec. The reactor is a 1 cm inner diameter, 20.8 cm long stainless steel tube containing 3.6 g of KN(SiMe₃)₂ on 3.6 g of glass wool. After passing of liquid trisilane through the flow reactor, the products are collected in the dry ice trap (175.5 g), followed by liquid nitrogen trap (2.7 g). The gas and liquid phases of the traps were analyzed by GC. The contents of the dry ice trap were distilled. 1.7 g of nonvolatile liquid was obtained from the dry ice trap. The nonvolatile liquid was a mixture of silanes with 6 and more silicon atoms [GC]. 173.8 g of volatile silanes were obtained from the dry ice trap. The volatile silanes were a mixture of silanes Si_(n)H_(2n+2) (n=1-8). The non-volatile liquid was a mixture of silanes with 6 and more silicon atoms [GC]. FIG. 6 is a gas chromatogram of the volatile liquid products distilled from the dry ice trap after one pass of liquid Si₃H₈ through the KN(SiMe₃)₂ to catalyst. The results are summarized in the Tables 12 and 13 below.

TABLE 12 Results of flow reaction applying the liquid trisilane and KN(SiMe₃)₂. Si₃H₈ Selectivity: n- Residence Precursor consumed Si₄H₁₀:i- Yield: n- Yield: time content (g) (g) Si₄H₁₀ Si₄H₁₀ % Si₅H₁₂ % P (psig) (Seconds) (178.2 g) 34.9 7.7:1 6.8 1.7 27.2 ± 0.5 310-587 [99.8% Av. = 467 Si₃H₈]

TABLE 13 Mass balance, Yield in g/mol. Yield of Products Volatile g (precursor i- n- Si₅H₁₂ Heavies ≥ Non Precursor mixture)/Mol SiH₄ Si₂H₆ Si₄H₁₀ Si₄H₁₀ (total) Si6 volatile 99.8% 178.2 g 2.69 g 11.89 g, 1.53 g 12.06 g 3.06 g 0.85 g 1.8 g Si₃H₈ 1.926 mol 0.08 mol 0.19 mol 0.013 mol 0.01 mol 0.020 mol Si₃H₈ Normalized 4.35% 9.92% 0.65% 5.11% 1.04% — — to 100% Si₃H₈ in mol

KN(SiMe₃)₂ is significantly active in flow reaction with the liquid trisilane and produces a low amount of nonvolatile silanes.

The present example illustrates a potential for scaling.

Example 9 Gaseous Si₃H₈ and Na (35%) on Silica

The Experiments were performed on a similar setup as in Example 3. The results of the experiments are provided in Table 14.

TABLE 14 Results of Trisilane passing through Na (35%) on silica. n- Gas phase Liquid phase (%) Si₄H₁₀/ Heavies ≥ T g g (mmol) i- n- i- Si6 Lost ° C. Si₃H₈ Liq. SiH₄ Si₂H₆ Si₃H₈ Si₃H₈ Si₄H₁₀ Si₄H₁₀ Si₅H₁₂ Si₄H₁₀ (%) (g) 60 1.69 1.67 0.2 0.06 0.59 98.9 0.2 0.7 0.2 3.5 0.02 0.02 95 1.79 1.75 0.09 0.03 0.59 99.3 0.1 0.4 0.07 4 0.10 0.04 118 1.81 1.81 0.07 0.02 0.58 99.4 0.1 0.4 0.13 4 0.16 0 205 1.66 1.51 0.58 0.08 0.59 99.1 0.15 0.5 0.15 3.3 0.11 0.15 250 1.54 0.82 1.66 0.14 0.60 98.8 0.2 0.7 0.20 3.5 0.02 0.72

While these results are not as selective for n-Si₄H₁₀ as the results obtained using Vitride™ on Silica or KN(SiMe₃)₂, they remain better than the results obtained from the prior art catalysts of Comparative Examples 1 and 2.

Example 10 Gaseous Si₃H₈ and Na₂O on Alumina

The experiments were performed on a similar setup as in Example 3. The results of the experiments are provided in Table 15.

TABLE 15 n- Gas phase Liquid phase (%) Si₄H₁₀/ Heavies ≥ T g g (mmol) i- n- i- Si6 Lost ° C. Si₃H₈ Liq SiH₄ Si₂H₆ Si₃H₈ Si₃H₈ Si₄H₁₀ Si₄H₁₀ Si₅H₁₂ Si₄H₁₀ (%) (g) 150 1.91 1.76 *2.56 0.16 0.59 98.0 0.3 1.2 0.4 4 0.05 0.15 150 1.84 1.85 1.13 0.13 0.58 98.4 0.3 1.0 0.3 2.5 0.03 −0.01 200 1.92 1.81 1.36 0.20 0.59 98.6 0.4 0.8 0.2 2 0.02 0.11 250 1.82 1.71 1.70 0.25 0.59 98.7 0.3 0.8 0.2 2.7 0.02 0.11 *High value of SiH₄ and weight gain in the first experiment might be due to reaction of Si₃H₈ with the surface OH giving SiH₄ and OSi₂H₅.

While these results are not as selective for n-Si₄H₁₀ as the results obtained using Vitride™ on Silica or KN(SiMe₃)₂, they remain better than most of the results obtained from the prior art catalysts of Comparative Examples 1 and 2.

Example 11 Gaseous Si₃H₈ and KH

The experiments were performed on a similar setup as in Example 3. The results of the experiments are provided in Table 6.

TABLE 16 n- Gas phase Liquid phase (%) Si₄H₁₀/ Heavies ≥ T g g (mmol) i- n- i- Si6 Lost ° C. Si₃H₈ Liq SiH₄ Si₂H₆ Si₃H₈ Si₃H₈ Si₄H₁₀ Si₄H₁₀ Si₅H₁₂ Si₄H₁₀ (%) (g) 63 1.74 1.76 0.03 0.03 0.58 99.3 0.1 0.4 0.17 4.0 0.021 −0.01* 154 1.76 1.76 0.1 0.04 0.58 99.0 0.17 0.5 0.28 2.9 0.073 0 251 1.74 1.71 0.91 0.31 0.58 97.3 0.7 1.6 0.35 2.3 0.084 0.03 310 1.42 0.66 0.97 0.29 0.59 96.5 0.8 2.0 0.58 2.5 0.12 0.76** *Negative values might be due to insufficient precision and deviation of zero weight. **Weight loss in part is due to application of vacuum to remove H₂ during the passage of Si₃H₈.

Example 12 Tetrasilane Shelflife Study

A shelf life study was performed to verify that the fixed ratio of 2 tetrasilane isomers remains stable at room temperature and 35° C. Tetrasilane obtained from a pyrolysis process was stored at room temperature in multiple containers. Another container was stored at 35° C. The liquid contents were measured by GC over time.

A 6 L aluminum cylinder was vacuum baked at 52° C. and 4.4×10⁻⁶ Torr. 50 mL stainless steel vessels were vacuum baked at approximately 200° C. and 50 mTorr. 1.2 L stainless steel bubblers were vacuum baked at approximately 150° C. and 85 mTorr. The list of the containers under investigation and the amount of Tetrasilane in them are presented in Table 17.

TABLE 17 Total Si₄H₁₀ n-Si₄H₁₀ Package Volume (L) load (g) % w/w* n-Si₄H₁₀:i-Si₄H₁₀ ^(†) 1.2 L 1.2 325 70.96 2.46 ± 0.04 (RT) 1.2 L 1.2 383 70.70 2.44 ± 0.01 (35° C.) 6 L 5.9 384 70.96 2.48 ± 0.02 50 cc 0.05 6.8 78.61 3.78 ± 0.05 coated 50 cc not 0.05 6.5 78.61 3.75 ± 0.05 coated *Starting amount on day 1 ^(†)average ratio and standard deviation during the whole duration of experiment.

FIG. 7 is a graph of the n-Si₄H₁₀:i-Si₄H₁₀ ratio over time at ambient temperature.

FIG. 8 is a graph of the n-Si₄H₁₀:i-Si₄H₁₀ ratio in a 1.2 L stainless steel bubbler over time at room temperature (triangle) or 35° C. (square).

The ratio of isomers is similar in all experiments within 400 days, the deviation is below 2%, highest deviation of n-Si₄H₁₀:i-Si₄H₁₀ ratio is 1.9% for 55 cc non coated vessel, demonstrating the stability of compositions over time for vapor deposition.

The compositions for stability test contained 70-79% w/w of n-Si₄H₁₀ and 21-29% of i-Si₄H₁₀. We anticipate that the compositions with 90-95% w/w of n-Si₄H₁₀ will behave in the same way, since the difference with the reported composition is 10-20% of n-Si₄H₁₀.

Comparative Example 3 Halide Concentration of Commercially Available n-Tetrasilane

Commercially available n-tetrasilane from the catalog of an established commercial n-tetrasilane vendor was analyzed by GC. The commercially available product contains 34.3% w/w of i-Si₄H₁₀ and 64.1% w/w of n-Si₄H₁₀, while the total amount of Si₄H₁₀ is 98.4% w/w, and it contains Si₂H₆ 0.1% w/w, Si₃H₈ 0.5% w/w, Si₅H₁₂ 0.6% w/w, Si₆H₁₄ 0.3% w/w, Si₇H₁₆ 0.1% w/w. The ratio n-S₄H₁₀:i-Si₄H₁₀=1.9:1. Such composition i-Si₄H₁₀/n-Si₄H₁₀ together with lower and higher silanes might create a vapor pressure drift over time due to the different boiling points of i-Si₄H₁₀ and n-Si₄H₁₀, lower and higher silanes. This may result in the irreproducible growth per cycle rate, which is not acceptable for a vapor deposition process.

While embodiments of this invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit or teaching of this invention. The embodiments described herein are exemplary only and not limiting. Many variations and modifications of the composition and method are possible and within the scope of the invention.

Accordingly the scope of protection is not limited to the embodiments described herein, but is only limited by the claims which follow, the scope of which shall include all equivalents of the subject matter of the claims. 

What is claimed is:
 1. A method of selectively synthesizing n-tetrasilane, the method comprising: producing a silane mixture having a n-Si₄H₁₀:i-Si₄H₁₀ ratio ranging from approximately 5:1 to approximately 15:1 by reacting a Si_(n)H_((2n+2)) reactant, wherein n=1-3, with a heterogeneous catalyst selected from a Group I, II or III element from the Periodic Table or oxides, alkyls, hydrides, silanides, or silyl amides thereof, and wherein the only catalyst used in the reaction is the heterogeneous catalyst selected from a Group I, II or III element from the Periodic Table or oxides, alkyls, hydrides, silanides, or silyl amides thereof.
 2. The method of claim 1, wherein the Si_(n)H_((2n+2)) reactant is Si₃H₈.
 3. The method of claim 2, wherein the Si_(n)H_((2n+2)) reactant is liquid Si₃H₈.
 4. The method of claim 1, wherein the Si_(n)H_((2n+2)) reactant is a mixture of Si₂H₆ and Si₃H₈.
 5. The method of claim 1, wherein the heterogeneous catalyst is selected from the group consisting of LiAlH₄, LiAlH_(n)R_(4−n), NaAlH_(n)R_(4−n), KAlH_(n)R_(4−n), RbAlH_(n)R_(4−n), CsAlH_(n)R_(4−n), and combinations thereof, wherein n=1, 2,or 3 and each R is independently C_(m)H_(2m+1) with m=1-10 or an aliphatic group having an oxygen or nitrogen atom.
 6. The method of claim 5, wherein the heterogeneous catalyst is sodium bis(2-methoxyethoxy)aluminum hydride.
 7. The method of claim 6, wherein the ratio of n-Si₄H₁₀:i-Si₄H₁₀ ranges from approximately 8:1 to approximately 15:1.
 8. The method of claim 1, wherein the heterogeneous catalyst is a Group I metal and Group I metal oxide.
 9. The method of claim 1, wherein the heterogeneous catalyst is a metal silylamide catalyst.
 10. The method of claim 9, wherein the metal silylamide catalyst is sodium bis(trimethylsilyl)am ide.
 11. The method of claim 9, wherein the metal silylamide catalyst is potassium bis(trimethylsilyl)amide.
 12. The method of claim 11, wherein the ratio of n-Si₄H₁₀:i-Si₄H₁₀ ranges from approximately 8:1 to approximately 15:1.
 13. The method of claim 1, wherein the heterogeneous catalyst is a metal silanide catalyst.
 14. The method of claim 13, wherein the metal silanide catalysti is KSiPh₃.
 15. The method of claim 1, further comprising isolating the n-Si₄H₁₀:i-Si₄H₁₀ mixture from a Si_(a)H_((2a+2)) mixture, wherein a=1-6.
 16. The method of claim 1, further comprising fractionally distilling the n-Si₄H₁₀:i-Si₄H₁₀ silane mixture to produce a Si-containing film forming composition comprising approximately 95% w/w to approximately 100% w/w n-Si₄H₁₀.
 17. A method of selectively synthesizing n-tetrasilane, the method comprising: producing a n-Si₄H₁₀:i-Si₄H₁₀ silane mixture having a ratio ranging from approximately 5:1 to approximately 12:1 by catalyzing liquid Si₃H₈ using a catalyst selected from the group consisting of sodium, sodium oxide, sodium bis(2-methoxyethoxy)aluminum hydride, potassium bis(trimethylsilyl)amide (KN(SiMe₃)₂), lithium aluminum hydride (LiAlH₄), potassium triphenyl silicon (KSiPh₃), potassium hydride (KH), and mixtures thereof, wherein the only catalyst used in the reaction is selected from the group consisting of sodium, sodium oxide, sodium bis(2-methoxyethoxy)aluminum hydride, potassium bis(trimethylsilyl)amide (KN(SiMe₃)₂), lithium aluminum hydride (LiAlH₄), potassium triphenyl silicon (KSiPh₃), potassium hydride (KH), and mixtures thereof.
 18. The method of claim 16, further comprising isolating the n-Si₄H₁₀:i-Si₄H₁₀ mixture from a Si_(a)H_((2a+2)) mixture, wherein a=1-6.
 19. The method of claim 17, further comprising fractionally distilling the n-Si₄H₁₀:i-Si₄H₁₀ silane mixture to produce a Si-containing film forming composition comprising approximately 95% w/w to approximately 100% w/w n-Si₄H₁₀. 